CA2111056C - Low sediment process for forming borated dispersant - Google Patents

Abstract

A low sediment process for forming a borated oil soluble polymer-substituted nitrogen- or ester-containing lubricating oil additive. A non-borated polymer-substituted nitrogen- or ester-containing additive in the presence of a solvent therefor, is contacted under boronating reaction conditions in a reaction zone with particulate boric acid. The boric acid has an average particle size distribution in lubricating oil characterized by a .slzero. value of not greater than about 450.
The .slzero. value is the ratio of said particles' total spherical volume divided by said particles' total spherical external surface area.

Description

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IMPROVED LOW SEDIMENT PROCESS
FOR FORMING BORATED DISPERSANT (PT-849) BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION
This invention relates to the preparation of borated lubricating oil additives, and more specifically to the preparation of borated nitrogen-containing polymeric lubricating oil additives.
BRIEF DESCRIPTION OF THE PRIOR ART
Borated lubricating oil additives of many types have been proposed for use in lubricating oils. Principal among these are borated nitrogen-containing polymer lubricating oil additives such as dispersants, which are typically prepared by reacting a polymeric nitrogen-containing dispersant with a boronating agent, such as boric acid. Conventional borated dispersants include borated polyisobutenyl succinimides and borated Mannich base dispersants which are themselves prepared by borating a Mannich base reaction product derived from polyalkyl-substituted phenols, aldehyde and polyamine.
For example, when the nitrogen-containing dispersant comprises polyisobutenyl succinimide, it can be reacted with boric acid; water is evolved and the resulting salt product is the borated polyalkene succinimide. However, the above reactions also yield undesirable by-products, which are oil insoluble species which are generally required to be removed from the borated lubricating oil additive before it is either sold or incorporated into either fully formulated lubricating oils or into concentrates (so-called "adpacks" which are concentrates containing a variety of selected components). These oil insoluble species are detectable by adding solvent (normally at a 50 volume o level) to the product and spinning the dilute product in a centrifuge tube. These insoluble species are generally measured as a volume percent of the total graduated centrifuge tube.
U.S. Patent 3,087,936 is directed to the preparation of a reaction product of an aliphatic olefin polymer succinic acid or anhydride with an amine, followed by reacting the resulting product with a boron compound, such as boric acid.
U.S. Patent 3,313,727 is directed to the preparation of stable dispersions of alkali metal borates in lubricating oil wherein a hydrated alkali metal borate is admixed with an emulsifying agent in an amount sufficient to maintain the borate particles as stable dispersion.
The particles are said to be almost entirely less than 1 micron in size and, for the most part, less than 0.5 microns. Suitable alkali metal borates are metaborates and tetraborates of sodium and potassium having from 1 to 4 waters of hydration. Neutral dispersants such as alkenyl succinimides of alkaline amines can also be present in these compositions.
U.S. Patent 4,025,445 relates to boron amide lubricating oil additives which are obtained by mixing a chlorinated hydrocarbon with an alkylene polyamine to form a nitrogen-containing reaction product which is then combined with a boron compound for reaction of the boron compound with the nitrogen-containing reaction product.
The additive thus formed is disclosed to be effective as an antirust crankcase lubricating oil additive. The boron compounds which were said to be useful include boron oxide, boron trifluoride, boron tribromide, boron trichloride and boric acid. Examples in this patent illustrate the use of an unspecified powdered anhydric boric acid, and filtering of the resulting boric reaction product.
U.S. Patent 4,419,387 is directed to preparation of a boric acid having improved handling properties. The patentee discloses that in the manufacture of boric acid, crystals of fine particle size (less than about 75 microns in size) are generally separated from the product, since these fines are unsuitable for most customers due to their dustiness and difficult handling properties. The patentee contacts boric acid particles with gaseous ammonia to reduce the lubricity of the boric acid crystals. Use of such reduced lubricity boric acid crystals in glass manufacture is disclosed. U.S. Patent 4,487,803 contains a similar disclosure.
U.S. Patent 4,578,086 is directed to a method for controlling boric acid particle size distributions for boric acid crystallized from saturated aqueous feed solutions thereof. It is disclosed that crystal in boric acid prepared from prior art processes generally are of amine particle size of about 190 to about 195 microns or less, and that this mole size causes problems with subsequent purification, handling and storage. The patentee employs a water soluble acrylamide homopolymer or copolymer in the aqueous solution from which the boric acid is crystallized in order to increase the mean particle size of the crystal and boric acid.
U.S. Patent 4,801,404 is related to boric acid suspensions useful for biocide components and wood preservatives and as fire retardant components for wood treatments, which comprise concentrated, finely dispersed suspensions of boric acid and a small amount of soluble borate salt in an aqueous medium. The patentee contrasts the patent's suspension with prior art highly concentrated to solutions of boric acid and water soluble amines or polyamines, and points out that the amine components interferes in many uses in that this component is additionally introduced into the resulting mixtures to which the concentrated boric acid solution is applied.
U.S. Patent 4,834,913 relates to an apparatus and method for forming finely divided dry boric acid.
SUMMARY OF THE INVENTION
The process of the present invention provides an improved low sediment borated lubricating oil product useful in lubricating oil concentrates and fully formulated lubricating oils. The improved low sediment process comprises (a) contacting a polymer-substituted nitrogen- or ester-containing or metal salt or metal complex containing additive in the presence of a solvent therefor, under boronating reaction conditions in a reaction zone charged with boric acid having a particle size distribution in lubricating oil characterized by a m value (hereinafter defined) of not greater than about 450 microns, and preferably less than 430 microns, (wherein said m value is the ratio of said charged particles' total spherical volume divided by said charged particles' total spherical external surface area: wherein the total spherical volume is the sum of all sphere volumes of formula (4/3)Nt~d3 of each of a plurality of distribution segments and the total spherical external surface is the sum of all sphere surface areas of formula Nnd2 of each said distribution segment; wherein for each said segment, N is the particle volume percent of the segment and d is the average particle diameter:' and (b) recovering a borated oil soluble polymer-substituted nitrogen- or ester-containing lubricating oil additive.

-4a-According to one aspect of the present invention, there is provided an improved low sediment process for forming a borated oil soluble polymer-substituted nitrogen- or ester-containing lubricating oil additive which comprises (a) contacting a non-borated polymer-substituted nitrogen- or ester-containing additive in the presence of a solvent therefore, under boronating reaction conditions in a reaction zone with particulate boric acid having an average particle size distribution in lubricating oil characterized by a Q~
value of not greater than 450, wherein said QJ value is the ratio of said particles' total spherical volume divided by said particles' total spherical external surface area, and (b) recovering said borated additive.

a CA 02111056 2003-08-11 In accordance with a preferred embodiment, a polyalkenyl-substituted succinimide dispersant additive is contacted in lubricating oil with boric acid having the above recited average particle size characteristics.
A particularly preferred product in accordance with the process of this invention is a borated oil soluble polyisobutylene-substituted nitrogen- or ester-containing lubricating oil dispersant additive.
It has been found that borated lubricating oil additives can be formed with such improved low sediment employing characteristics by the process of the present invention, in contrast to the high sediment levels which result from the use of boric acid particles having a m value of greater than about 500. A useful determination of volume corrected average particle diameter is referred to in a brochure, Brinkmann Particle Size Analyzer, Available Difference in Size and Shape Analysis, Brinkmann Instruments, Inc., 1988; and a useful apparatus and method for such determination is presented in Brinkmann, PSA 2010 Particle Size Analyzer, Operation Manual, Version 4.2 (July 1989) published by Brinkmann Instruments, Inc. and/or Galai Production, Ltd.
DETAILED DESCRIPTION OF THE INVENTION
The polymer-substituted nitrogen- or carboxylic or thiol ester-containing or metal salt or metal complex containing additive employed in the present invention can comprise at least one dispersant adduct formed by reacting a reactive amine compound or a hydroxy-containing organic compound with long chain hydrocarbon-substituted reactant comprising at least one member selected from the group consisting of;

(A) long chain hydrocarbons substituted with mono-or dicarboxylic acid, anhydride or ester groups, or thiol ester;
(B) halogenated long chain hydrocarbons;
(C) mixtures of formaldehyde and a long chain hydrocarbyl-substituted phenol; and (D) mixtures of formaldehyde and a reaction product formed by reaction of long chain hydrocarbons substituted with mono- or dicarboxylic acid, anhydride or ester groups and an amino-substituted, optionally hydrocarbyl-substituted phenol.
Useful and preferred polymer dispersants are disclosed in U.S. Patent No. 5,102,566.-The homopolymers and copolymers useful in the present invention can be conveniently characterized based on molecular weight range. Polymers and copolymers of low, intermediate and high molecular weights can be prepared.
Low molecular weight polymers are considered to be polymers having a number average molecular weight of less than 20,000, preferably from 500 to 5,000, more preferably from 1,000 to 5,000 and most preferably from 1,500 to 5,000. The low molecular weights are number average molecular weights measured by vapor phase osmometry. Low molecular weight polymers are useful in forming dispersants for lubricant additives.

Medium molecular weight materials having a number average molecular weight range of from 5,000 to 200,000, preferably 10,000 to 50,000; and more preferably, from 20,000 to 100,000 and most preferably from 25,000 to 80,000 are useful for viscosity index improvers for lubricating oil compositions. The medium number average molecular weights can be determined by membrane osmometry.
AMINE COMPOUND
The polymer-substituted nitrogen-containing additive employed in the present invention is prepared by contacting a long chain hydrocarbon substituted reactant with an amine compound containing at least two (e. g., from 2 to 20), preferably at least 3 (e.g., from 3 to 15), and most preferably from 3 to 8, reactive nitrogen moieties (that is, the total of the nitrogen-bonded H
atoms) per molecule of the amine compound. The amine compound will generally comprise at least one member selected from the group consisting of ammonia, organic primary monoamines and organic polyamines containing at least one primary amine group or at least two secondary amine groups per molecule. Generally, the organic amines will contain from about 2 to 60, preferably 2 to 40 (e.g., 3 to 20), total carbon atoms and about 2 to 12, preferably 3 to 12, and most preferably from 3 to 8 (e. g., 5 to 9) total nitrogen atoms in the molecule.
These amines may be hydrocarbyl amines or may be hydrocarbyl amines including other groups, e.g, hydroxy groups, alkoxy groups, amide groups, nitriles, imidazoline groups, and the like. Hydroxy amines with 1 to 6 hydroxy groups, preferably 1 to 3 hydroxy groups are particularly useful. Preferred amines are aliphatic _8_ saturated amines, including those of the general formulas:
R-N-R', and R-N-(CH2)s N-(CH2)s N-R
R" R' R " ' t R' (I) (II) wherein R, R', R " and R " ' are independently selected from the group consisting of hydrogen; C1 to C25 straight or branched chain alkyl radicals; C1 to C12 alkoxy; C2 to C6 alkylene radicals; C2 to C12 hydroxy amino alkylene radicals; and C1 to C12 alkylamino; C2 to C6 alkylene radicals; and wherein R"' can additionally comprise a moiety of the formula:
(CH2)s' i H (III) t' R' wherein R' is as defined above, and wherein s and s' can be the same or a different number of from 2 to 6, preferably 2 to 4; and t and t' can be the same or different and are numbers of from 0 to 10, preferably 2 to 7 , and most preferably about 3 to 7 , with the proviso that the sum of t and t' is not greater than 15. To assure a facile reaction, it is preferred that R, R', R" , R" ' , s, s' , t and t' be selected in a manner sufficient to provide the compounds of Formulas I and II
with typically at least one primary or secondary amine group, preferably at least two primary or secondary amine groups. This can be achieved by selecting at least one of said R, R', R" or R " ' groups to be hydrogen or by letting t in Formula II be at least one when R"' is H or when the III moiety possesses a secondary amino group.

_g-Non-limiting examples of suitable organic amine compounds include: 1,2-diaminoethane; 1,3-diaminopropane; 1,4-diaminobutane; 1,6-diaminohexane;
polyethylene amines such as diethylene triamine;
triethylene tetra; tetraethylene pentamine; polypropylene amines such as 1,2-propylene diamine; di-(1,2-propylene)triamine; di-(1,3-propylene) triamine; N,N-dimethyl-1,3-diaminopropane; N,N-di-(2-aminoethyl) ethylene diamine; N,N-di(2-hydroxyethyl)-1,3-propylene diamine: 3-dodecyloxypropylamine; N-dodecyl-1,3-propane diamine; tris hydroxymethylaminomethane (THAM);
diisopropanol amine; diethanol amine; triethanol amine;
mono-, di-, and tri-tallow amines; amino morpholines such as N-(3-aminopropyl)morpholine; and mixtures thereof.
Other useful amine compounds include: alicyclic diamines such as 1,4-di(aminomethyl) cyclohexane, and heterocyclic nitrogen compounds such as imidazolines, and N-aminoalkyl piperazines of the general formula (IV):

H- NH-(CH2) N N (CH2)p2 NH -H
pl y /
nl CH2CH2 n2 n3 wherein pl and p2 are the same or different and are each integers of from 1 to 4, and nl, n2 and n3 are the same or different and are each integers of from 1 to 3. Non-limiting examples of such amines include 2-pentadecyl imidazoline: N-(2-aminoethyl) piperazine; etc.
Commercial mixtures of amine compounds may advantageously be used. For example, one process for preparing alkylene amines involves the reaction of an alkylene dihalide (such as ethylene dichloride or propylene dichloride) with ammonia, which results in a complex mixture of alkylene amines wherein pairs of nitrogens are joined by alkylene groups, forming such compounds as diethylene triamine, triethylenetetra, tetraethylene pentamine and isomeric piperazines. Low cost poly(ethyleneamines) compounds averaging about 5 to 7 nitrogen atoms per molecule are available commercially under trade names such as "Polyamine H"* "Polyamine 400";~"Dow Polyamine E-100"* etc.
Useful amines also include polyoxyalkylene polyamines such as those of the formulae:
NH2 alkylene (--O-alkylene-) m-NH2 (V) where m has a value of about 3 to 70 and preferably 10 to 35; and R4 [-alkylene (~-alkylene)n4 NH2]p (VI) where "n4" has a value of about 1 to 40 with the provision that the sum of all the n4's is from about 3 to about 70 and preferably from about 6 to about 35, and R4 is a polyvalent saturated hydrocarbon radical of up to 10 carbon atoms wherein the number of substituents of the R4 group is represented by the value of "p", which is a number of from 3 to 6. The alkylene groups in either formula (V) or (VI) may be straight or branched chains containing about 2 to 7, and preferably about 2 to 4 carbon atoms.
The polyoxyalkylene polyamines of formulas (V) or (VI) above, preferably polyoxyalkylene diamines and polyoxyalkylene triamines, may have average molecular weights ranging from about 200 to about 4,000 and preferably from about 400 to about 2,000. The preferred polyoxyalkylene polyamines include the polyoxyethylene and polyoxypropylene diamines and the polyoxypropylene triamines having average molecular weights ranging from about 200 to 2,000. The polyoxyalkylene polyamines are * Trade-mark commercially available and may be obtained, for example, from the Jefferson Chemical Company, Inc. under the trade name "Jeffamines* D-230, D-400, D-1000, D-2000, T-403", etc.
The amine compound can comprise an amido-amine as described in U.S. Patent 4,857,217. Such amido-amines can be formed by reacting a polyamine with an alpha, beta-ethylenically unsaturated compound (e. g., of formula XXII), e.g., by reacting polyethylene amines (e. g., tetraethylene pentaamine, pentaethylene hexamine, and the like), polyoxyethylene and polyoxypropylene amines, e.g., polyoxypropylene diamine, trismethylolaminomethane and pentaerythritol, and combinations thereof, with an acrylate-type compound, and most preferably with an acrylate-type reactant selected from the group consisting of lower alkyl alky-acrylates (e. g., methyl, ethyl, isopropyl, propyl, isobutyl, n-butyl, tert-butyl, etc., esters of methacrylic acid, acrylic acid, and the like).
Exemplary of such amido-amines are compounds of the formula:
NH2L(CH2)vNH~uC(0)C2H4LNH(CH2)vluNH2 wherein a is an integer of from 1 to 10, and v is an integer of from 2 to 6.
Most preferred as the amine compound are members selected fram the group consisting of ammonia and organic diprimary amines having from 2 to 12 carbon atoms and from 2 to 8 nitrogen atoms per molecule. Examples of such preferred organic diprimary amines are ethylene diamine, propylene diamine, diethylene triamine, dipropylene triamine, triethylene tetraamine, * Trade-mark tripropylene tetraamine, tetraethylene pentaamine, tetrapropylene pentaamine, polyhexamethylene diamine, phenyl diamine.
Additional amines useful in the present invention are described in U.S. Patent 3,445,441, (A) Acid/ester Substituted Long Chain Hydrocarbons The long chain hydrocarbyl polymer-substituted mono-or dicarboxylic acid reactants, i.e., acid, anhydride or acid ester used in this invention, includes the reaction product of a long chain hydrocarbon polymer, generally a polyolefin, with a monounsaturated carboxylic reactant comprising at least one member selected from the group consisting of (i) monounsaturated C4 to Clp dicarboxylic acid (preferably wherein (a) the carboxyl groups are vicinyl, (i.e. located on adjacent carbon atoms) and (b) at least one, preferably both, of said adjacent carbon atoms are part of said mono unsaturation); (ii) derivatives of (i) such as anhydrides or C1 to C5 alcohol derived mono- or diesters of (i); (iii) monounsaturated C3 to Clp monocarboxylic acid wherein the carbon-carbon double bond is conjugated to the carboxy group, i.e, of the structure o -C=C-C- ;

and (iv) derivatives of (iii) such as C1 to C5 alcohol derived monoesters of (iii). Upon reaction with the polymer, the monounsaturation of the monounsaturated carboxylic reactant becomes saturated. Thus, for example, malefic anhydride becomes a polymer substituted succinic anhydride, and acrylic acid becomes a polymer substituted propionic acid. Also useful are the derivatives of the above acids with thiol-containing compounds which can be analogs of the alcohols with S
substituted for 0. Preferred thiols include alkyl thiols including C1 to C5 and preferably C2 to C5 alkyl thiols.
Typically, from about 0.7 to about 4.0 (e.g., 0.8 to 2.6), preferably from about 1.0 to about 2.0, and most preferably from about 1.1 to about 1.7 moles of said monounsaturated carboxylic reactant are charged to the reactor per mole of polymer charged.
Normally, not all of the polymer reacts with the monounsaturated carboxylic reactant and the reaction mixture will contain non-acid substituted polymer. The polymer-substituted mono- or dicarboxylic acid material (also referred to herein as "functionalized" polymer or polyolefin), non-acid substituted polyolefin, and any other polymeric by-products, e.g. chlorinated polyolefin, (also referred to herein as "unfunctionalized" polymer) are collectively referred to herein as "product residue"
or "product mixture". The non-acid substituted polymer is typically not removed from the reaction mixture (because such removal is difficult and would be commercially infeasible) and the product mixture, stripped of any monounsaturated carboxylic reactant is employed for further reaction with the amine or alcohol as described hereinafter to make the dispersant.

Characterization of the average number of moles of monounsaturated carboxylic reactant which have reacted per mole of polymer charged to the reaction (whether it has undergone reaction or not) is defined herein as functionality. Said functionality is based upon (i) determination of the saponification number of the resulting product mixture using potassium hydroxide; and (ii) the number average molecular weight of the polymer charged, using techniques well known in the art.
Functionality is defined solely with reference to the resulting product mixture. Although the amount of said reacted polymer contained in the resulting product mixture can be subsequently modified, i.e., increased or decreased by techniques known in the art, such modifications do not alter functionality as defined above. The terms "polymer-substituted monocarboxylic acid material" and "polymer-substituted dicarboxylic acid material" as used herein are intended to refer to the product mixture whether it has undergone such modification or not.
Accordingly, the functionality of the polymer substituted mono- and dicarboxylic acid material will be typically at least about 0.5, preferably at least about 0.8, and most preferably at least about 0.9 and will vary typically from about 0.5 to about 2.8 (e.g., 0.6 to 2), preferably from about 0.8 to about 1.4, and most preferably from about 0.9 to about 1.3.
Exemplary of such monounsaturated carboxylic reactants are fumaric acid, itaconic acid, malefic acid, malefic anhydride, chloromaleic acid, chloromaleic anhydride, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and lower alkyl (e. g., C1 to C4 alkyl) acid esters of the foregoing, e.g., methyl maleate, ethyl fumarate, methyl fumarate, etc.

Preferred olefin polymers for reaction with the monounsaturated carboxylic reactants to form reactant A
are polymers comprising a major molar amount of C2 to C10, e.g. C2 to C5 monoolefin. Such olefins include ethylene, propylene, butylene, isobutylene, pentene, octene-1, styrene, etc. The polymers can be homopolymers such as polyisobutylene, as well as copolymers of two or more of such olefins such as copolymers of: ethylene and propylene: butylene and isobutylene; propylene and isobutylene; etc. Mixtures of polymers prepared by polymerization of mixtures of isobutylene, butene-1 and butene-2, e.g., polyisobutylene wherein up to about 40%
of the monomer units are derived from butene-1 and butene-2, is an exemplary, and preferred, olefin polymer.
Other copolymers include those in which a minor molar amount of the copolymer monomers, e.g., 1 to 10 mole %, is a C4 to Clg non-conjugated diolefin, e.g., a copolymer of isobutylene and butadiene; or a copolymer of ethylene, propylene and 1,4-hexadiene; etc.
In some cases, the olefin polymer may be completely saturated, for example an ethylene-propylene copolymer made by a Ziegler-Natta synthesis using hydrogen as a moderator to control molecular weight.
The olefin polymers used in the formation of dispersant additives will have number average molecular weights within the range of about 300 to 10,000, generally from about 700 and about 5,000, preferably from about 1,000 to 4,000, more preferably between about 1,300 and about 3,000. Particularly useful olefin polymers have number average molecular weights within the range of about 1,500 and about 3,000 with approximately one terminal double bond per polymer chain. An especially useful starting material for highly potent dispersant additives useful in accordance with this invention is polyisobutylene, wherein up to about 40% of the monomer units are derived from butene-1 and/or butene-2. The number average molecular weight for such polymers can be determined by several known techniques. A convenient method for such determination is by gel permeation chromatography (GPC) which additionally provides molecular weight distribution information, see W. W. Yau, J. J. Kirkland and D. D. Bly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979.
The olefin polymers will generally have a molecular weight distribution (the ratio of the weight average molecular weight to number average molecular weight, i.e.
M n/ M n) of from about 1.0 to 4.5, and more typically from about 1.5 to 3Ø
The polymer can be reacted with the monounsaturated carboxylic reactant by a variety of methods. For example, the polymer can be first halogenated, chlorinated or brominated to about 1 to 8 wt. %, preferably 3 to 7 wt. % chlorine, or bromine, based on the weight of polymer, by passing the chlorine or bromine through the polymer at a temperature of 60 to 250°C, preferably 110 to 160°C, e.g., 120 to 140°C, for about 0.5 to 10, preferably 1 to 7 hours. The halogenated polymer may then be reacted with sufficient monounsaturated carboxylic reactant at 100 to 250°C, usually about 180° to 235°C, for about 0.5 to 10, e.g., 3 to 8 hours, so the product obtained will contain the desired number of moles of the monounsaturated carboxylic reactant per mole of the halogenated polymer. Processes of this general type are taught in U.S. Patents 3,087,436; 3,172,892; 3,272,746 and others.
Alternatively, the polymer and the monounsaturated carboxylic reactant are mixed and heated while adding chlorine to the hot material. Processes of this type are disclosed in U.S. Patents 3,215,707; 3,231,587;
3,912,764; 4,110,349; 4,234,435; and in U.K. 1,440,219.
Alternately, the polymer and the monounsaturated carboxylic reactant can be contacted at elevated temperature to cause a thermal "ene" reaction to take place. Thermal "ene" reactions have been heretofore described in U.S. Patents 3,361,673 and 3,401,118, Preferably, the polymers used in this invention contain less than 5 wt. %, more preferably less than 2 wt. %, and most preferably less than 1 wt. % of a polymer fraction comprising polymer molecules having a molecular weight of less than about 300, as determined by high temperature gel permeation chromatography employing the corresponding polymer calibration curve. Such preferred polymers have been found to permit the preparation of reaction products, particularly when employing malefic anhydride as the unsaturated acid reactant, with decreased sediment. In the event the polymer produced as described above contains greater than about 5 wt. % of such a low molecular weight polymer fraction, the polymer can be first treated by conventional means to remove the low molecular weight fraction to the desired level prior to initiating the ene reaction, and preferably prior to contacting the polymer with the selected unsaturated carboxylic reactant(s). For example, the polymer can be heated, preferably with inert gas (e. g., nitrogen) stripping, at elevated temperature under a reduced pressure to volatilize the low molecular weight polymer components which can then be removed from the heat treatment vessel. The precise temperature, pressure and time for such heat treatment can vary widely depending on such factors as the polymer number average molecular weight, the amount of the low molecular weight fraction to be removed, the particular monomers employed and other factors. Generally, a temperature of from about 60 to 100°C and a pressure of from about 0.1 to 0.9 atmospheres and a time of from about 0.5 to 20 hours (e.g., 2 to 8 hours) will be sufficient.
In this process, the selected polymer and monounsaturated carboxylic reactant and halogen (e. g., chlorine gas), where employed, are contacted for a time and under conditions effective to form the desired polymer substituted mono- or dicarboxylic acid material.
Generally, the polymer and monounsaturated carboxylic reactant will be contacted in an unsaturated carboxylic reactant to polymer mole ratio usually from about 0.7:1 to 4:1, and preferably from about 1:1 to 2:1, at an elevated temperature, generally from about 120 to 260°C, preferably from about 160 to 240°C. The mole ratio of halogen to monounsaturated carboxylic reactant charged will also vary and will generally range from about 0.5:1 to 4:1, and more typically from about o.7:1 to 2:1 (e. g., from about 0.9 to 1.4:1). The reaction will be generally carried out, with stirring for a time of from about 1 to 20 hours, preferably from about 2 to 6 hours.
By the use of halogen, about 65 to 95 wt. % of the polyolefin, e.g. polyisobutylene will normally react with the monounsaturated carboxylic acid reactant. Upon carrying out a thermal reaction without the use of halogen or a catalyst, then usually only about 50 to 75 wt. % of the polyisobutylene will react. Chlorination helps increase the reactivity. For convenience, the aforesaid functionality ratios of mono- or dicarboxylic acid producing units to polyolefin, e.g., 1.1 to 1.8, etc. are based upon the total amount of polyolefin, that is, the total of both the reacted and unreacted polyolefin, used to make the product.

The reaction is preferably conducted in the substantial absence of o2 and water (to avoid competing side reactions), and to this end can be conducted in an atmosphere of dry N2 gas or other gas inert under the reaction conditions. The reactants can be charged separately or together as a mixture to the reaction zone, and the reaction can be carried out continuously, semi-continuously or batchwise. Although not generally necessary, the reaction can be carried out in the presence of a liquid diluent or solvent, e.g., a hydrocarbon diluent such as mineral lubricating oil, toluene, xylene, dichlorobenzene and the like. The polymer substituted mono- or dicarboxylic acid material thus formed can be recovered from the liquid reaction mixture, e.g., after stripping the reaction mixture, if desired, with an inert gas such as N2 to remove unreacted unsaturated carboxylic reactant.
If desired, a catalyst or promoter for reaction of the olefin polymer and monounsaturated carboxylic reactant (whether the olefin polymer and monounsaturated carboxylic reactant are contacted in the presence or absence of halogen (e.g., chlorine)) can be employed in the reaction zone. Such catalyst of promoters include alkoxides of Ti, Zr, V and A1, and nickel salts (e.g., Ni acetoacetonate and Ni iodide) which catalysts or promoters will be generally employed in an amount of from about 1 to 5, 000 ppm by weight, based on the mass of the reaction medium.

(B) Halodenated Long Chain Hydrocarbons Also useful as long chain hydrocarbyl reactants to form the improved dispersants of this invention are halogenated long chain aliphatic hydrocarbons (as shown in U.S. Patents 3,275,554, 3,438,757, 3,565,804 and 4,000,353, where the halogen group on the halogenated hydrocarbon is displaced with the reactive amine compound in the subsequent reaction therewith. For example, a polymer of a C2 to C5 monoolefin, e.g., polyethylene, polypropylene or polyisobutylene, wherein the polymer has an average molecular weight within the range of from 600 to about 3,000, preferably from about 800 to about 2,500, is halogenated with either bromine or chlorine;
preferably the latter. The halogen may be conveniently added as gaseous chloride, liquid bromine, or a hydrohalogen, e.g., HC1 or HBr gas.
The amount of halogen introduced will depend on the particular hydrocarbon used, the desired amount of amine to be introduced into the molecule, the particular alkylene amine used, and the halogen used. The amount of halogen introduced will generally be in the range of from about 1 to 5 halogen atoms per molecule, depending on the reactivity of the resulting halide. On a weight percent basis, the amount of halide will generally range from about 1 to 25, more usually from about 1 to 10.
The halogenation step may be conducted in the temperature. range of from about ordinary ambient temperatures to about 120°C. To aid in the halogenation step, the polymer may be dissolved in a suitable solvent, such as carbon tetrachloride, in order to lower the viscosity of the polymer, although the use of such a solvent is not necessary.

The time required for halogenation may be varied to some extent by the rate at which the halogen is introduced. Ordinarily from about 2 to about 5 hours is a satisfactory halogenation period. In a representative plant scale operation involving the chlorination of polyisobutylene of 830 molecular weight, a 100-pound batch will be chlorinated with 10 pounds of chlorine introduced into the reactor over a period of 3 1/2 hours with a chlorination temperature of about 120°C.
The halohydrocarbon and amine compound (e. g., alkylene polyamine or polyalkylene polyamine) may be brought together neat or in the presence of an inert solvent, particularly a hydrocarbon solvent. The inert hydrocarbon solvent may be aliphatic or aromatic. Also, aliphatic alcohols may be used by themselves or in combination with another solvent, when capable of dissolving the reactants.
The reaction may be carried out at room temperature (20°C), but elevated temperatures are preferred.
Usually, the temperature will be in the range of from about 100° to 225°C. For minimum sediment formation a preferred amination temperature range is from 115° to 135°C. Depending on the temperature of the reaction, the particular halogen used, the mole ratios and the particular amine, as well as the reactant concentrations, the time may vary from 1 to 24 hours, more usually from about 3 to 20 hours. Times greatly in excess of 24 hours do not particularly enhance the yield and may lead to undesirable degradation. It is therefore preferred to limit the reaction time to fewer than 24 hours.
The mole ratio of halohydrocarbon to amine compound will generally be in the range from about 0.2 to 10 moles of amine compound per mole of halohydrocarbon, more usually 0.5 to 5 moles of amine compound per mole of halohydrocarbon. The mole ratio will depend upon the amount of halogen present in the halohydrocarbon, the particular halogen and the desired ratio of hydrocarbon to amine compound.
Small amounts of residual halogen in the final composition are not deleterious. Generally, the residual halogen, as bound halogen, will be in the range of 0 to wt. ~ of the composition. Small amounts of halogen may be present as the hydrohalide salt of the hydrocarbon substituted alkylene polyamines.
Generally, the hydrocarbons used will have aliphatic unsaturation. In particular instances, the amines may react in a way resulting in the elimination of hydrogen halide, introducing further aliphatic unsaturation into the hydrocarbon radical. Therefore, the hydrocarbon radicals usually will be olefinically unsaturated.
However, the olefinic unsaturation does not significantly affect the utility of the product, and when available, saturated aliphatic halide may be used.
After the reaction has been carried out for a sufficient length of time, the reaction mixture may be extracted with a hydrocarbon medium to free the product from any low molecular weight amine salt which has formed. The product may then be isolated by evaporation of the solvent. Further separation from unreacted hydrocarbon or purification may be carried out as desired, e.g., chromatography.
(C) Mixtures of Formaldehyde and Lonct Chain Hvdrocarbon Substituted Phenol Another class of long chain hydrocarbyl reactants to form the improved dispersants of this invention are any of the long chain hydrocarbyl-substituted hydroxy aromatic compounds which are known in the art as useful for forming Mannich condensation products. Such Mannich condensation products generally are prepared by condensing about 1 mole of a high molecular weight hydrocarbyl substituted hydroxy aromatic compound (e. g., having a number average molecular weight of 700 or greater) with about 1 to 2.5 moles of an aldehyde such as formaldehyde or paraformaldehyde and about 0.5 to 2 moles of the reactive amine compound, using the condensation conditions as disclosed, e.g., in U.S. Patents 3,442,808:
3,649,229; and 3,798,165.
Such Mannich condensation products may include a long chain, high molecular weight hydrocarbon on the phenol group or may be reacted with a compound containing such a hydrocarbon, e.g., polyalkenyl succinic anhydride as shown in said aforementioned U.S. Patent 3,442,808.
The optionally substituted hydroxy aromatic compounds used in the preparation of the Mannich base products include those compounds having the formula Rly - Ar - (OH)Z
wherein Ar represents R2x~ R2x O
o q or o wherein q is 1 or 2, R1 is a long chain hydrocarbon, R2 is a hydrocarbon or substituted hydrocarbon radical having from 1 to about 3 carbon atoms or a halogen radical such as the bromide or chloride radical, y is an integer from 1 to 2 , x is an integer from 0 to 2 , and z is an integer from 1 to 2.
Illustrative of such Ar groups are phenylene, biphenylene, naphthylene and the like.
The long chain hydrocarbon R21 substituents are olefin polymers as described above for those olefin polymers useful informing reactants.
Representative hydrocarbyl substituted hydroxy aromatic compounds contemplated for use in the present invention include, but are not limited to, 2-polypropylene phenol, 3-polypropylene phenol, 4-polypropylene phenol, 2-polybutylene phenol, 3-polyisobutylene phenol, 4-polyisobutylene phenol, 4-polyisobutylene-2-chlorophenol, 4-polyisobutylene-2-methylphenol, and the like.
Suitable hydrocarbyl-substitued polyhydroxy aromatic compounds include the polyolefin catechols, the polyolefin resorcinols, and the polyolefin hydroquinones, e,g,, 4-polyisobutylene-1,2-dihydroxybenzene, 3-polypropylene-1,2-dihydroxybenzene, 5-polyisobutylene-1,3-dihydroxybenzene, 4-polyamylene-1,3-dihydroxybenzene, and the like.
Suitable hydrocarbyl-substituted naphthols include 1-polyisobutylene-5-hydroxynaphthalene, 1-polypropylene-3-hydroxynaphthalene and the like.
(D) Mannich Base Condensation Products Still another class of long chain hydrocarbyl reactants to form the improved dispersants of this invention are the Mannich base aminophenol-type condensation products as they are known in the art. Such Mannich condensation products generally are prepared by reacting about 1 mole of long chain hydrocarbon substituted mono and dicarboxylic acids or their anhydrides (e. g., polyisobutylene-substituted succinic anhydride) with an about 1 mole of amine-substituted hydroxy aromatic compound (e. g., aminophenol), which aromatic compound can also be halogen- or hydrocarbyl-sustituted, to form a long chain hydrocarbon substituted amide or imide-containing phenol intermediate adduct (generally having a number average molecular weight of 700 or greater) , and condensing about a molar proportion of the long chain hydrocarbon substituted amide- or imide-containing phenol intermediate adduct with about 1 to 2.5 moles of formaldehyde and about 0.5 to 2 moles of the second adduct of this invention.
Suitable aminophenols include 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-amino-3-methylphenol, 4-amino-3-chlorophenol, 4-amino-2-bromophenol and 4-amino-3-ethylphenol.
The preparation and use of the hydroxy aromatic compounds and amino-substituted hydroxy aromatic compounds, and methods useful for reaction thereof with an aldehyde and the selected amine or alcohol are as described in U.S. Patents 4,820,432 and 4,828,742;
The selected reactive amine compound (e.g., an alkylene polyamine) is readily reacted with the selected polymer substituted mono- or dicarboxylic acid material, e.g., alkenyl succinic anhydride, by heating an oil solution containing 5 to 95 wt.% of the polymer substituted dicarboxylic acid' material to about 100 to 250°C., preferably 125 to 175°C., generally for 1 to 10, e.g., 2 to 6 hours until the desired amount of water is removed. The heating is preferably carried out to favor formation of imides and/or amides, rather than salts.
Generally from 1 to 5, preferably from about 1.5 to 3 moles of mono- or dicarboxylic acid moiety content (e. g., grafted malefic anhydride or grafted acrylic acid content) is used per reactive nitrogen equivalent (preferably per equivalent of primary nitrogen) of the amine compound.
Preferably, the polymer substituted mono- or dicarboxylic acid producing material and amine compound will be contacted for a time and under conditions sufficient to react substantially all of the primary nitrogens in the second adduct reactant. The progress of this reaction can be followed by infra-red analysis.
The dispersant-forming reaction can be conducted in a polar or non-polar solvent (e. g., xylene, toluene, benzene and the like), and is preferably conducted in the presence of a mineral or synthetic lubricating oil.
The ester-containing dispersant additive employed in this invention can be derived by reacting the aforesaid long chain hydrocarbon substituted dicarboxylic acid material and one or more hydroxy compounds such as monohydric and polyhydric alcohols or aromatic compounds such as phenols and naphthols, etc. The polyhydric alcohols are the most preferred hydroxy compound and preferably contain from 2 to about 10 hydroxy radicals, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and other alkylene glycols in which the alkylene radical contains from 2 to about 8 carbon atoms. Other useful polyhydric alcohols include glycerol, mono-oleate of glycerol, monostearate of glycerol, monomethyl ether of glycerol, pentaerythritol, dipentaerythritol, and mixtures thereof.
The ester dispersant may also be derived from unsaturated alcohols such as allyl alcohol, cinnamyl alcohol, propargyl alcohol, 1-cyclohexane-3-ol, and oleyl alcohol. Still other classes of the alcohols capable of yielding the ester dispersants comprise the ether-alcohols and amino-alcohols including, for example, the oxy-alkylene, oxy-arylene-, amino-alkylene-, and amino-arylene-substituted alcohols having one or more oxy-alkylene, amino-alkylene or amino-arylene oxy-arylene radicals. They are exemplified by Cellosolve, Carbitol, N,N,N',N'-tetrahydroxy-trimethylene di-amine, and ether-alcohols having up to about 150 oxy-alkylene radicals in which the alkylene radical contains from 1 to about 8 carbon atoms.
The ester dispersant may be di-esters of succinic acids or acidic esters, i.e., partially esterified succinic acids; as well as partially esterified polyhydric alcohols or phenols, i.e., esters having free alcohols or phenolic hydroxyl radicals. Mixtures of the above illustrated esters likewise are contemplated within the scope of this invention.
The ester dispersant may be prepared by one of several known methods as illustrated for example in U.S.
Patent 3,381,022.
Hydroxyamines which can be reacted with the aforesaid long chain hydrocarbon substituted dicarboxylic acid materials to form dispersants include 2-amino-1-bu-tanol, 2-amino-2-methyl-1-propanol, p-(beta-hydroxy-ethyl)-aniline, 2-amino-1-propanol, 3-amino-1-propanol, 2-amino-2-methyl-1, 3-propane-diol, 2-amino-2-ethyl-1, 3-propanediol, N-(beta-hydroxy-propyl)-N'-(beta-amino-' CA 02111056 2004-05-13 ethyl)-piperazine, tris(hydroxymethyl) amino-methane (also known as trismethylolaminomethane), 2-amino-1-butanol, ethanolamine, beta-(beta-hydroxyethoxy)ethylamine, and the like. Mixtures of these or similar amines can also be employed.
Preferred in the present invention are polymer-substituted nitrogen-containing dispersant additives.
Most preferred are polyisobutenyl succinimide dispersants.
Boric acid which is charged to the boration reaction zone in the process of the present invention is preferably substantially anhydrous, and will generally contain less than about 0.2 wt.% of water, preferably from about 0.1 to 0.2 wt.% water. The particles of boric acid can be characterized by a m value of not greater than about 450 (e. g., typically from about 300 to 450), and preferably not greater than about 430. Smaller m values are preferred.
The o value, as used in the present invention, is the ratio of the total spherical volume occupied by boric acid particles in synthetic or petroleum oil, typically a neutral normal point petroleum base stock, to the total spherical area by the boric acid particles wetted by petroleum base stock. This parameter (i.e., w) is calculated by utilizing raw statistical data provided by the Brinkmann* Particle Size Analyzer Model 2010 (manufactured by Galia Instruments of Israel). The description of the method of obtaining data, the particle size analyzer and statistical treatment of the data is presented in the Brinkmanri brochure and operating manual *Trade-mark referred to above. Such data is provided as probability volume particle population density (percent ranges) Generally, the Brinkmann particle size analyzer operates as follows. A particle flows through a ring or cylinder of monochromatic light and interrupts the beam.
If the particle passes through the beam cleanly, the diameter measurement is accepted. If it passes through the beam partially, it is rejected. Diameter is corrected for the particles velocity. Particles are assumed to be spherical, but are aspect ratio, the ratio of the length to the width, can be inputted to correct for non-spherical shapes. A microscopic video camera is built in to verify spherical geometry of the sample. In all cases, the boric acid particles detected closely approximated spheres. Sample concentration is important.
Samples with too high a concentration give noisy signals and excessive rejection rate of particles. Samples which are too dilute give excessively long acquisition times and possibly non-representative population sampling. The rate slurry or suspension is pumped through the flow cell and based upon desired input population size to the machine, the analyzer will continue to count accepted particles until the desired population size is achieved.
The machine can also be programmed to take multiple acquisitions to accumulate a more statistically significant population size. The raw number data is accumulated and normalized to give an output which correctly assigns the particle size profile of the population corrected for volume, area and actual numbers of particles.
The preferred instrument (Brinkmann 2010, Particle Size Analyzer) uses a focused scanning-laser spot and a simple time-domain analysis (time of transition) to measure particle diameters precisely, from 0.5 to 1200 The range can vary for smaller particles. In accordance with the boric acid of the present, the range is from 0.05 to 600. The time-of-transition principle states that when a scanning laser beam moving at a fixed velocity (v_) is measured for the time (t) it takes to cross the diameter of any particle, the distance (d) or particle diameter can be calculated.
v_ x t = a A He-Ne laser beam passes through a spinning 1°
wedge prism which rotates the beam at a constant velocity, creating a 600 ~ diameter scanning circle. The beam passes through a microscope objective, creating a 1.2 ~ "spot" focused within the sample cell. The focal plane, the laser spot, and the scanning circle define the measuring zone.
The rotating beam continues through the sample cell and falls on a PIN photodiode that measures the beam's intensity. A particle moving through the measuring zone interrupts the beam, causing an interactive pulse or "shadow" on the photodiode. The duration time (t) of interaction coupled with the rotational speed (v_) of the prism (and beam) sets up the equation for the measurement of the distance (d). Each time of transition is directly mapped to its corresponding diameter. The rapid speed of the moving beam renders particles "stationary", eliminating sources of error due to particle movement.
Signals from an out-of-focus or off-center interaction can create statistical errors. The time from the beginning of an interaction to the point of darkest occlusion of light (rise time) is measured The time it takes the beam to cross the chord of the particle (time of transition) is measured.
Out-of-focus or off-center interactions generate rise times that are too long in proportion to the particle diameter. Using an algorithm based on the overall pulse signature with normalized rise-time criteria, each interaction is accepted or rejected. Only data from accepted signals are filed for analysis.
Data can be presented as number, area and volume.
Particle size based on the projected volume or mass can be determined preferably using a number distribution.
Such a determination is important for characterizing the boric acid, since sediment formations can be affected by a "number" of too large particles which may not be appreciated based a mass or volume average.
The parameter ~ is arrived at by (1) taking the average particle diameter in each particle diameter range reported by the Brinkman Particle Size Analyzer (for example, 3 microns is the average diameter in a range of 2 to 4 microns, 5 microns is the average diameter in a range of 4 to 6 microns, etc.). (2) calculating the weighted volume and area of a sphere with that diameter in each range . ( 3 ) summing up all of the segments up to 600 microns for the volume and the area, respectively.
(4) Divide these two sum values to get the ratio characterizing the ~ parameter.
These distributions are all normalized to 100% of all of the particles by the Brinkman instrument program or, to look at it another way, they are on a 100 particle basis. The volume and area of each segment can be determined as follows:
Sphere volume = (N1) (4/3) (d3) (fl) sphere surface Area = (N1)(d2)(fl) wherein N1 is the number of particles in the distribution segment and d is the average particle diameter microns in a distribution segment.

The distribution segments employed for calculating cover particles ranging in size from 5 to 600 microns.
The distribution segments are 4-6, 6-8, 8-10, 10-14, 14-20, 20-30, 30-40, 40-50, 50-60, 60-70, 70-80, 80-90, 90-100, 100-150, 150-200, 200-300, 300-400, 400-500, and 500-600 microns.
Accordingly, the parameter ~ can be defined in terms of following equation:
total spherical volume Ei(4/3)Nindi3 _ __________________-________-__ _ ______________ total spherical surface area ~iNindi2 wherein, for each of a plurality of distribution segments defining a particle size range, di is the average particle diameter for the ith distribution segment; Ni is the particle volume percent of the ith distribution segment: and the sum is taken over all the segments. The distribution segments i are the segments defined in the preceding paragraph.
As should be clear from the above equation, the parameter has the dimensions of length (i.e., microns) and is a type of volume-weighted particle diameter.
Consequently, the ~ value is sensitive to, and therefore reflects, the presence of relatively large-sized particles in a boric acid sample. Because the formation of sediment byproduct in the boration of lubricating oil additives can be affected by the presence of large particles (e. g., 500 to 600 microns) in the boric acid employed, the ~ parameter is a useful means for screening and/or identifying boric acid materials which can minimize sediment formation. Accordingly, the improved low sediment process of the invention employs boric acid having a ~ value of not greater than about 450.

Boric acid samples can of course contain particles having diameters less than 5 microns and/or greater than 600 microns. For the purpose of calculating ~, boric acid particles less than 5 microns in diameter are ignored because of their relatively insignificant impact on per cent volume measurements. Thus, the Brinkmann Particle size Analyzer is programmed not to measure their diameters and the particles are not included in the particle size distribution. On the other hand, boric .
acid particles having diameters greater than 600 microns can be included in the determination of ~. If the sample contains particle sizes greater than 600 microns, the sample is processed to separate the large-sized particles prior to the size analysis. The size analysis is then conducted using the Brinkmann analyzer, or other instrument or technique providing an equivalent analysis, only on the portion of the sample containing particle sizes less than 600 microns. The resulting particle distribution is then adjusted to account for the particles greater than 600 microns before calculating the value.
Before analysis the boric acid should be first passed, dry (less than 0.2 wt.~ max. water), through a 40 mesh sieve to selectively remove particles sizes greater than 600 microns. The calculation for particle size can be adjusted by making an assumption that the screened particles have an assigned particle size (i.e., 600 microns). If 10 more percent of the particles are accrued (i.e., by a 40 mesh sieve), this amount is assigned a 600 micron particle size.
The sample of boric acid to be used in the Brinkmann particle size analyzer should be a slurry in oil. The concentration should be sufficient in order to operate the instrument. Sample preparation is reviewed in the of boric acid in neutral mineral oil is preferred. The type of oil is not critical and can be petroleum base stock or synthetic oil.
It is preferred to analyze boric acid particle size in the presence of a lubricating oil basestock. It has been found there is good visual evidence for the phenomenon of particle agglomeration: that is, smaller particles have an affinity for larger particles because of the interparticle hydrogen bonding enhanced by the surrounding non-polar solution which repels the boric acid. Therefore, methods of analysis that rely on dry boric acid (for example, methods which rely on particle size distributions by fluidizing the boric acid in gas streams and passing it through a particle detection system) do not correlate well with such oil-slurry methods of analysis. Slurrying the boric acid in oil gives a more accurate characterization of the particle distribution. This is particularly the case here where the oil can be the actual reaction solvent. Particle agglomeration can occur at different distributions particularly those having mixtures of fine and large particles.
Boration Reaction The selected nitrogen- or ester-containing or metal salt or complex containing dispersant additive and particulate boric acid can be charged separately or in combination to a reaction zone, and the process of the present invention can be carried out in a continuous, semicontinuous or batchwise process. Any conventional apparatus may be employed, and stirred tank reactors and tubular reactors are preferred.

The boration reaction can be carried out in the presence of a solvent or inert diluent for the nitrogen-or ester-containing dispersant. Suitable solvents and inert diluents include mineral lubricating oils, hydrocarbon solvents (e. g., zylene, toluene, benzene, ethylbenzene, and the like) mineral lubricating oil, and synthetic oil with mineral lubricating oils preferred.
Excess liquid polymer can be a co-solvent.
The amount of the particulate boric acid charged to the reaction zone can vary widely. Generally, the particulate boric acid will be charged to the boration reaction zone in an amount of from about 0.35 to 5 parts by weight, preferably from about 0.35 to 2.8 parts by weight, and most preferably from about .7 to 1.0 parts by weight of the particulate boric acid, per part by weight of the nitrogen-containing or ester-containing polymer additive charged to the boration reaction zone. Based on atomic boron content, there is 2, preferably 0.05 to 1.0 and more preferably 0.1 to 0.5 parts of boron per part of polymer additive. The range of boric acid contemplates one mole of boric acid per mole of functional group of the polymer additive. For nitrogen -containing polymer additives the amount of boric acid is based on the secondary nitrogen content. The above range contemplates two secondary nitrogens per molecule (polyamine).
The addition of boric acid above stoichiometric ratio is considered to be overboration. This process is particularly adaptable to accomplishing "high boron" or "overboration".
A wide variety of temperature and other reaction conditions can be employed in the boration reaction zone.
Generally, a temperature of from about 100 to 170 °C, preferably from about 110 to 150°C, and more preferably from about 125 to 135°C, will be employed. The pressure in the boration reaction zone can be atmospheric, sub-atmospheric or super-atmospheric, and atmospheric pressures preferred. A useful pressure range is from 0 to 7000 kPa.
In order to avoid undesired side reactions, the boration reaction zone is preferably purged with nitrogen or other inert gas to exclude air and oxygen gas from above the surface of the liquid reaction medium.
However, this is not essential, and good results can be obtained in the presence of air. While the boration reaction can be conducted in air, it is preferred to use an inert atmospheric to prevent oxidation of the base stock.
Experimental results indicate that it is preferred not to strip water off before the reaction. Removal of too much water can lead to boric acid liquidation.
Generally, it is preferred not to strip out water before or after reaction.
The selected nitrogen-containing or ester-containing dispersant and particulate boric acid can be charged to the boration reaction zone in any order. Generally, for ease of handling of the reactants, it is preferred that the nitrogen-containing or ester-containing dispersant, and any solvent or inert diluent, be first charged to the boration reaction vessel (for example, a stirred tank vessel), followed by addition of the particulate boric acid to the liquid reaction medium with stirring.
Stirring of a stirred tank vessel can be accomplished by any conventional means, and the degree of mixing will depend upon the density and viscosity of the liquid reaction medium, the size of the liquid reaction medium, and the stirred tank, the degree of baffeling within the stirred tank vessel, the rate of addition (and the amount of) the particulate boric acid charged, the precise temperature and the desired reaction time, and other factors. Generally, however, any of the conventional stirred tank vessel stirring devices can be employed, such as retreat blade stirs, impellers, high shear mixer/dispenser, a swirl box, static mixers, and the like.
The reactants can be charged to the boration reaction zone intermittently, continuously or in a batchwise manner. The reaction zone itself can comprise one reaction vessel or a series of reaction vessels. The reaction vessel can itself be provided with conventional temperature control means. For example, the reaction vessel can be provided with internal heating or cooling coils, with liquid pump-around loops, wherein a portion of the liquid reaction medium is withdrawn, passed to an external heat exchanger and then returned to the reaction liquid for temperature control, and other conventional means.
In the preferred commercial granular boric acid particles, typically having average particle size grater than 1200, (~ > 1200) are mechanically reduced, preferably in a fluidized jet mill. The jet mill fluidized the particle bed causes the interaction of the fluidized particles. The particle size is thereby reduced to the ranges useful in the present invention.
The milled particles are mixed with from 50 to 80 % by weight of oil txo form a slurry. The slurry can reacted as recited above.
Following the completion of the desired reaction time, the low sediment borated dispersant product can be withdrawn from the boration reaction zone and employed directly in the formulation of lubricating oil concentrates and/or fully formulated lubricating oils.
The borated dispersants of the present invention are characterized and provide low sediment level. Generally, the borated products of the present invention will contain sediment in an amount less than 0.03 vol.%, preferably less than 0.025 (e.g., from about trace to 0.03 vol.%), more preferably less than about 0.02 vol.%
(e.g. , from about trace to 0.02 vol. %) , A modified ASTM
(77-073) test, using heptane solvent) also referred to as a BS&W (Boron Sediment and Water) centrifuge procedure can be used to measure the amount of sediment.
The borated dispersant or multifunctional viscosity index improver can be used in a wide variety of lubricating oils.
Lubricating Compositions The primary utility for all the above-described post-treated functionalized and/or derivatized polymer, is as and additive for oleaginous compositions. For ease of discussion the above-mentioned material is referred to herein as additives) when used in the context of an oleaginous composition containing such "additive(s)".
Accordingly, the additives of the present invention may be used by incorporation and dissolution into an oleaginous material such as fuels and lubricating oils.
When the additives of this invention are used in normally liquid petroleum fuels such as middle distillates boiling from about 65°C to 430°C, including kerosene, diesel fuels, home heating fuel oil, jet fuels, etc., a concentration of the additives in the fuel in the range of typically from about 0.001 to about 0.5, and preferably 0.005 to about 0.15 wt. %, based on the total weight of the composition, will usually be employed.

Useful compositions and additives are disclosed in U.S.
Patent No. 5,102,566, hereby incorporated by reference.
The additives of the present invention find their primary utility in lubricating oil compositions which employ a base oil in which the additives are dissolved or dispersed therein. Such base oils may be natural or synthetic. Base oils suitable for use in preparing the lubricating oil compositions of the present invention include those conventionally employed as crankcase lubricating oils for spark-ignited and compression-ignited internal combustion engines, such as automobile and truck engines, marine and railroad diesel engines, and the like. Advantageous results are also achieved by employing the additive mixtures of the present invention in base oils conventionally employed in and/or adapted for use as power transmitting fluids, universal tractor fluids and hydraulic fluids, heavy duty hydraulic fluids, power steering fluids and the like. Gear lubricants, industrial oils, pump oils and other lubricating oil compositions can also benefit from the incorporation therein of the additives of the present invention.
These lubricating oil formulations conventionally contain several different types of additives that will supply the characteristics that are required in the formulations. Among these types of additives are included viscosity index improvers, antioxidants, corrosion inhibitors, detergents, dispersants, pour point depressants, antiwear agents, friction modifiers, etc.
The additives of the present invention, particularly those adapted for use as dispersants or viscosity modifiers, can be incorporated into a lubricating oil in any convenient way. Thus, they can be added directly to the oil by dispersing or dissolving the same in the oil at the desired level of concentrations of the additive.

Such blending into the additional lube oil can occur at room temperature or elevated temperatures.
Alternatively, the additives can be blended with a suitable oil-soluble solvent and base oil to form a concentrate, and then blending the concentrate with a lubricating oil basestock to obtain the final formulation. Such dispersant concentrates will typically contain (on an active ingredient (A. I.) basis) from about l0 to about 80 wt. %, typically about 20 to about 60 wt.
%, and preferably from about 40 to about 50 wt. %, additive, and typically from about 40 to 80 wt. %, preferably from about 40 to 60 wt. %, base oil, i.e., hydrocarbon oil based on the concentrate weight. The lubricating oil basestock for the additive typically is adapted to perform a selected function by the incorporation of additional additives therein to form lubricating oil compositions (i.e., formulations).
Usually these concentrates may be diluted with 3 to 100, e.g., 5 to 40 parts by weight of lubricating oil, per part by weight of the additive package, in forming finished lubricants, e.g. crankcase motor oils. The purpose of concentrates, of course, is to make the handling of the various materials less difficult and awkward as well as to facilitate solution or dispersion in the final blend. Thus, the additives of the present invention and formulations containing them would usually be employed in the form of a 40 to 50 wt. % concentrate, for example, in a lubricating oil fraction.
The additives of the present invention will be generally used in admixture with a lube oil basestock, comprising an oil of lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof. Useful oils are described in U.S. Patent Nos.
5,017,299 and 5,084,197.

Natural oils include animal oils and vegetable oils (e.g., castor, lard oil) liquid petroleum oils and hydrorefined, solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.
Synthetic lubricating oils include hydrocarbon oils and halosubstituted hydrocarbon oils such as polymerized and interpolymerized olefins (e. g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, etc.) poly(hexenes), poly(1-octenes), poly(1-decense), etc. and mixtures thereof;
alkylbenzenes (e. g., dodecyl-benzenes, tetradecyl-benzenes, dinonylbenzenes, di-(2-ethylhexyl)-benzenes, etc.): polyphenyls (e. g., biphenyls, terphenyls, alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof and the like.
Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc., constitute another class of known synthetic lubricating oils. These are exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e. g., methyl-poly isopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of polyethylene glycol having a molecular weight of 500 to 1,000, diethyl ether of polypropylene glycol having a molecular weight of 1,000 to 1,500; and mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C3 to Cg fatty acid esters and C13 Oxo acid diester of tetraethylene glycol.

Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e. g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, malefic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with a variety of alcohols (e. g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl)sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid.
Esters useful as synthetic oils also include those made from C5 to C12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.
Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxysiloxane oils and silicate oils comprise another useful class of synthetic lubricants; they include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-ethylhexyl)silicate, tetra-(p-tert-butylphenyl)silicate, hexa-(4-methyl-2-pentoxy) disiloxane, poly(methyl)siloxanes and poly(methyl-phenyl)siloxanes. Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e. g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.
Unrefined, refined and rerefined oils can be used in the lubricants of the present invention. Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from , distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil. Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques, such as distillation, solvent extraction, acid or base extraction, filtration and percolation are known to those skilled in the art. Rerefined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used in service. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for removal of spent additives and oil breakdown products.
Additional Formulation Components As indicated above, the additives of the present invention may be mixed with other types of additives selected to perform at least one desired function.
Typical of such formations are detergen/inhibitor, viscosity modification, wear inhibitor, oxidation inhibitor, corrosion inhibitor, friction modifier, foam inhibitor, rust inhibitor, demulsifier, lube oil flow improvers, and seal swell control. Each class of such additional additions is discussed in more detail below.
Deterqent/Inhibitor Metal-containing detergents which can also act as rust inhibitors hence the term "detergent/inhibitor" or simply "DI", include the metal salts of sulphonic acids, alkyl phenols, sulphurized alkyl phenols, alkyl salicylates, naphthenates, and other oil soluble mono-and dicarboxylic acids as well as metal-containing complexes thereof. Usually these metal-containing detergent/inhibitors are used in lubricating oil in amounts of about 0.01 to 10, e.g. 0.1 to 5 wt. %, based on the weight of the total lubricating composition.
Marine diesel lubricating oils typically employ such metal-containing rust inhibitors and detergents in amounts of up to about 20 wt. %.
Metal detergent/inhibitors are generally basic (viz, overbased) alkali or alkaline earth metal salts (or mixtures thereof, e.g, mixtures of Ca and Mg salts) of one or more organic sulfonic acid (generally a petroleum sulfonic acid or a synthetically prepared alkaryl sulfonic acid), petroleum naphthenic acids, alkyl benzene sulfonic acids, alkyl phenols, alkylene-bis-phenols, oil soluble fatty acids and the like, such as are described in U.S. Patent Nos. 2,501,731: 2,616,904: 2,616,905:
2,616,906; 2,616,911; 2,616,924; 2,616,925; 2,617,049:
2,777,874: 3,027,325; 3,256,186: 3,282,835: 3,384,585:
3,373,108: 3,350,308; 3,365,396: 3,342,733; 3,320,162;
3,312,618; 3,318,809 and 3,562,159. Among the petroleum sulfonates, the most useful products are those prepared by the sulfonation of suitable petroleum fractions with subsequent removal of acid sludge and purification. Synthetic alkaryl sulfonic acids are usually prepared from alkylated benzenes such as the Friedel-Crafts reaction product of benzene and a polymer such as tetrapropylene, Clg to C24 hydrocarbon polymer, etc. Suitable acids may also be obtained by sulfonation of alkylated derivatives of such compounds as diphenylene oxide thianthrene, phenolthioxine, diphenylene sulfide, phenothiazine, diphenyl oxide, diphenyl sulfide, diphenylamine, cyclohexane, decahydro naphthalene and the like.
The terms "basic salt" and "overbased salt" are used to designate metal salts wherein the metal is present in stoichiometrically larger amounts than the acid radical.
As used in this discussion, the term "complex"
refers to basic metal salts which contain metal in an amount in excess of that present in a neutral or normal metal salt. The "base number" of a complex is the number of milligrams of KOH to which one gram of the complex is equivalent as measured by titration.
The commonly employed methods for preparing the basic salts involve heating a mineral oil solution of the normal metal salt of the acid with a metal neutralizing agent. The use of a "promoter" in the neutralization step to aid the incorporation of a large excess of metal is known and is preferred for the preparation of such compositions.
Examples of compounds useful as the promoter include phenolic substances such as phenol, naphthol, alkyl phenols, thiophenol, sulfurized alkyl phenols, and condensation products of formaldehyde with a phenolic substance: alcohols such as methanol, 2-propanol, octanol, cellosolve, carbitol, ethylene glycol, stearyl alcohol and cyclohexanol; and amines such as aniline, phenylene diamine, phenothiazine, phenol beta-naphthylamine and dodecylamine.
The alkali and alkaline earth metal compounds which may be used in neutralizing these acids to provide the metal salts include the oxides and hydroxides, alkoxides, carbonates, carboxylate, sulfide, hydrosulfide, nitrate, borates and ethers of magnesium, calcium, and barium.
Examples are calcium oxide, calcium hydroxide, magnesium acetate and magnesium borate. As noted, the alkaline earth metal compound is used in excess of that required to complete neutralization of the alkaryl sulfonic acids.
Generally, the amount ranges from about 100 to 220%, although it is preferred to use at least 125%, of the stoichiometric amount of metal required for complete neutralization.
Various other preparations of basic alkaline earth metal alkaryl sulfonates are known, such as U.S. Patent Nos. 3,150,088 and 3,150,089 wherein overbasing is accomplished by hydrolysis of an alkoxide-carbonate complex with the alkaryl sulfonate in a hydrocarbon solvent-diluent oil.
An example of a convenient process for the preparation of the metal-containing complexes employs an oil-soluble sulfonic acid, such as a synthetically prepared didodecylbenzene sulfonic acid, which is mixed with an excess of lime (e.g., 10 equivalents per equivalent of the acid) and a promoter such as methanol, heptylphenol, or mixture thereof, and a solvent such as mineral oil, at 50°C to 150°C and the process mass is then carbonated until a homogeneous mass is obtained.
Complexes of sulfonic acids, carboxylic acids, and mixtures thereof are obtainable by processes such as are described in U.S. Patent No. 3,312,618. Another example is the preparation of a magnesium sulfonate normal magnesium salt thereof, an excess of magnesium oxide, water, and preferably also an alcohol such as methanol.
The carboxylic acids useful for preparing sulfonate carboxylate complexes, and carboxylate complexes, i.e., those obtainable from processes such as the above wherein a mixture of sulfonic acid and carboxylic acid or a carboxylic acid alone is used in lieu of the sulfonic acid, are oil-soluble acids and include primarily fatty acids which have at least about 12 aliphatic carbon atoms and not more than about 24 aliphatic carbon atoms.
Examples of these acids include: palmitic, stearic, myristic, oleic, linoleic, dodecanoic, behenic, etc.
Cyclic carboxylic acids may also be employed. These include aromatic and cycloaliphatic acids. The aromatic acids are those containing a benzenoid structure (i.e., benzene, naphthalene, etc.) and an oil-solubilizing radical or radicals having a total of at least about 15 to 18 carbon atoms, preferably from about 15 to about 200 carbon atoms. Examples of the aromatic acids include:
stearyl-benzoic acid, phenyl stearic acid, mono- or polywax-substituted benzoic or naphthoic acids wherein the wax group consists of at least about 18 carbon atoms, cetyl hydroxybenzoic acids, etc. The cycloaliphatic acids contemplated have at least about 12, usually up to about 30 carbon atoms. Examples of such acids are petroleum naphthenic acids, cetyl cyclohexane carboxylic acids, dilauryl decahydro naphthalene carboxylic acids, dioctyl cyclopentane carboxylic acids, etc. The thiocarboxylic acid analogs of the above acids, wherein one or both of the oxygen atoms of the carboxyl group are replaced by sulfur, are also contemplated.
The ratio of the sulfonic acid to the carboxylic acid in mixtures is typically at least 1:1 (on a chemical equivalent basis) and is usually less than 5:1, preferably from 1:1 to 2:1.

Usually, the basic composition obtained according to the above-described method is treated with carbon dioxide until its total base number (TBN) is less than about 50, as determined by ASTM procedure D-2896. In many instances, it is advantageous to form the basic product by adding a Ca or Mg base portionwise and carbonating after the addition of each portion. Products with very high metal ratios (10 or above) can be obtained by this method. As used herein, the term "metal ratio" refers to the ratio of total equivalents of alkaline earth metal in the sulfonate complex to equivalents of sulfonic acid anion therein. For example, a normal sulfonate has a metal ratio of 1.0 and a calcium sulfonate complex containing twice as much calcium as the normal salt has a metal ratio of 2Ø The overbased metal detergent compositions usually have metal ratios of at least about 1. 1, for example , from about 1. 1 to about 3 0 , with metal ratios of from about 2 to 20 being preferred.
Neutral metal sulfonates are frequently used as rust inhibitors. Polyvalent metal alkyl salicylate, naphthenate and phenate materials are known additives for lubricating oil compositions to improve their high temperature performance and to counteract deposition of carbonaceous matter on pistons (U.S. Patent No.
2,744,069). They can be methylene bridged or sulfur bridged.
The sulfurized metal phenates represent a preferred class of phenates and can be considered the "metal salt of a phenol sulfide" which thus refers to a metal salt whether neutral or basic. They can be typified by the general formula:

O
Y
OH OH
n (22) where x = 1 or 2, n = 0, 1 or 2; or a polymeric form of such a compound, where R is an alkyl radical, n and x are each integers from 1 to 4, and the average number of carbon atoms in all of the R groups is at least about 9 in order to ensure adequate solubility in oil. The individual R groups may each contain from 5 to 40, preferably 8 to 20, carbon atoms. The metal salt is prepared by reacting an alkyl phenol sulfide with a sufficient quantity of metal containing material to impart the desired alkalinity to the sulfurized metal phenate.
Regardless of the manner in which they are prepared, the sulfurized alkyl phenols which are useful generally contain from about 2 to about 14 wt. ~, preferably about 4 to about 12 wt. % sulfur based on the weight of sulfurized alkyl phenol.
The sulfurized alkyl phenol may also be converted by reaction with a metal containing material including oxides, hydroxides and complexes in an amount sufficient to neutralize said phenol and, if desired, to overbase the product to a desired alkalinity by procedures well known in the art. Preferred is a process of neutralization utilizing a solution of metal in a glycol ether.
The neutral or normal sulfurized metal phenates are those in which the ratio of metal to phenol nucleus is ._ 21 1 1056 about 1:2. The "overbased" or "basic" sulfurized metal phenates are sulfurized metal phenates wherein the ratio of metal to phenol is greater than that of stoichiometric, e.g. basic sulfurized metal dodecyl phenate, has a metal content up to and greater than 100%
in excess of the metal present in the corresponding normal sulfurized metal phenates wherein the excess metal is produced in oil-soluble or dispersible form (as by reaction with C02).
Magnesium and calcium containing detergents although beneficial in other respects can increase the tendency of the lubricating oil to oxidize. This is especially true of the highly basic sulphonates.
The magnesium and/or calcium is generally present as basic or neutral detergents such as the sulphonates and phenates.
Viscosity Modifiers A viscosity index (V.I.) improver, also referred to as viscosity modifier, is typically employed in multi-grade automobile engine lubricating oils. Viscosity modifiers impart high and low temperature operability to the lubricating oil and permit it to remain relatively viscous at elevated temperatures and also exhibit acceptable viscosity or fluidity at low temperatures.
Viscosity modifiers are generally high molecular weight hydrocarbon polymers including polyesters. The viscosity modifiers may include derivatized polymers recited above which include various properties or functions, including dispersancy properties. These oil soluble viscosity modifying polymers will generally have number average molecular weights of from 103 to 106, preferably 104 to 106, e.g., 20,000 to 250,000, as determined by gel permeation chromatography or osmometry.
Examples of suitable hydrocarbon polymers which can be used are viscosity improvers include homopolymers and copolymers of two or more monomers of C2 to C30, e.g. C2 to Cg olefins, including both alpha olefins and internal olefins, which may be straight or branched, aliphatic, aromatic, alkyl-aromatic, cycloaliphatic, etc.
Frequently they will be of ethylene with C3 to C30 olefins, particularly preferred being the copolymers of ethylene and propylene. Other polymers can be used such as polyisobutylenes, homopolymers and copolymers of C6 and higher alpha olefins, atactic polypropylene, hydrogenated polymers and copolymers and terpolymers of styrene, e.g. with isoprene and/or butadiene and hydrogenated derivatives thereof. The polymer may be degraded in molecular weight, for example, by mastication, extrusion, oxidation or thermal degradation, and it may be oxidized and contain oxygen. Also included are derivatized polymers such as post-grafted interpolymers of ethylene-propylene with an active monomer such as malefic anhydride which may be further reacted with an alcohol, or amine, e.g. an alkylene polyamine or hydroxy amine, e.g., see U.S. Patent Nos.
4,089,794: 4,160,739 and 4,137,185; or copolymers of ethylene and propylene reacted or grafted with nitrogen compounds such as shown in U.S. Patent Nos. 4,068,056;
4,068,058; 4,146,489 and 4,149,984.
Useful hydrocarbon polymers include ethylene copolymers containing from 15 to 90 wt. % ethylene, preferably 30 to 80 wt. % of ethylene and 10 to 85 wt. %, preferably 20 to 70 wt. % of one or more C3 to C2g, preferably C3 to Clg, more preferably C3 to Cg, alpha-olefins. While not essential, such copolymers preferably have a degree of crystallinity of less than 25 wt. %, as determined by X-ray and differential scanning calorimetry. Copolymers of ethylene and propylene or ethylene and butene are most preferred. Other alpha-olefins suitable in place of propylene to form the copolymer, or to be used in combination with ethylene and propylene, to form a terpolymer, tetrapolymer, etc., include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, etc.; also branched chain alpha-olefins, such as 4-methyl-1-pentene, 4-methyl-1-hexene, 5-methylpentene-1, 4,4-dimethyl-1-pentene, and 6-methylheptene-1, etc., and mixtures thereof.
Terpolymers, tetrapolymers, etc., of ethylene, said C3 to C2g alpha-olefin, and a non-conjugated diolefin or mixtures of such diolefins may also be used. The amount of the non-conjugated diolefin generally ranges from about 0.5 to 20 mole %, preferably from about 1 to about 7 mole %, based on the total amount of ethylene and alpha-olefin present.
The polyester V.I. improvers are generally polymers of esters of ethylenically unsaturated C3 to Cg mono- and dicarboxylic acids such as methacrylic and acrylic acids, malefic acid, malefic anhydride, fumaric acid, etc.
Examples of unsaturated esters that may be used include those of aliphatic saturated mono alcohols of at least 1 carbon atom and preferably of from 12 to 20 carbon atoms, such as decyl acrylate, lauryl acrylate, stearyl acrylate, eicosanyl acrylate, docosanyl acrylate, decyl methacrylate, diamyl fumarate, lauryl methacrylate, cetyl methacrylate, stearyl methacrylate, and the like and mixtures thereof.
Other esters include the vinyl alcohol esters of C2 to C22 fatty or mono carboxylic acids, preferably saturated such as vinyl acetate, vinyl laurate, vinyl palmitate, vinyl stearate, vinyl oleate, and the like and mixtures thereof. Copolymers of vinyl alcohol esters with unsaturated acid esters such as the copolymer of vinyl acetate with dialkyl fumarates, can also be used.
The esters may be copolymerized with still other unsaturated monomers such as olefins, e.g. 0.2 to 5 moles of C2 to C20 aliphatic or aromatic olefin per mole of unsaturated ester, or per mole of unsaturated acid or anhydride followed by esterification. For example, copolymers or styrene with malefic anhydride esterified with alcohols and amines are known, e.g., see U.S. Patent No. 3,702,300.
Such ester polymers may be grafted with, or the ester copolymerized with, polymerizable unsaturated nitrogen-containing monomers to impart dispersancy to the V.I. improvers. Examples of suitable unsaturated nitrogen-containing monomers include those containing 4 to 20 carbon atoms such as amino substituted olefins as p-(beta-diethylaminoethyl)styrene; basic nitrogen-containing heterocycles carrying a polymerizable ethylenically unsaturated substituent, e.g. the vinyl pyridines and the vinyl alkyl pyridines such as 2-vinyl-5-ethyl pyridine, 2-methyl-5-vinyl pyridine, 2-vinyl-pyridine, 4-vinylpyridine, 3-vinyl-pyridine, 3-methyl-5-vinyl-pyridine, 4-methyl-2-vinyl-pyridine, 4-ethyl-2-vinyl-pyridine and 2-butyl-1-5-vinyl-pyridine and the like. N-vinyl lactams are also suitable, e.g. N-vinyl pyrrolidones or N-vinyl piperidones. The vinyl pyrrolidones are preferred and are exemplified by N-vinyl pyrrolidone, N-(1-methylvinyl) pyrrolidone, N-vinyl-5-methyl pyrrolidone, N-vinyl-3, 3-dimethylpyrrolidone, N-vinyl-5-ethyl pyrrolidone, etc.
Such nitrogen- and ester-containing polymeric viscosity index improver dispersants are generally employed in concentrations of from about 0.05 to 10 wt.
in the fully formulated oil, and preferably from about 0.1 to 5 wt. %, and more preferably from about 0.5 to 3 wt. % can reduce (e.g., to about 0.5 wt. %) the amount of the ashless dispersant employed to provide the required dispersancy to the oil formulation.
Antiwear Agents Antiwear agents, as their name implies, reduce wear of moving metallic parts. Representative of conventional antiwear agents which may be used include, for example, the zinc dialkyl dithiophosphates, and the zinc diaryl dithiophosphates.
Suitable phosphates include dihydrocarbyl dithiophosphates, wherein the hydrocarbyl groups contain an average of at least 3 carbon atoms. Particularly useful are metal salts of at least one dihydrocarbyl dithiophosphoric acid wherein the hydrocarbyl groups contain an average of at least 3 carbon atoms. The acids from which the dihydrocarbyl dithiophosphates can be derived can be illustrated by acids of the formula:
S
R30_~P_S-H

wherein R3 and R4 are the same or different and are alkyl, cycloalkyl, aralkyl, alkaryl or substituted substantially hydrocarbon radical derivatives of any of the above groups, and wherein the R3 and R4 groups in the acid each have, on average, at least 3 carbon atoms.

._ 21 1 1056 By "substantially hydrocarbon" is meant radicals containing substituent groups (e. g., 1 to 4 substituent groups per radical moiety) such as ether, ester, vitro or halogen which do not materially affect the hydrocarbon character of the radical.
Specific examples of suitable R3 and R4 radicals include isopropyl,isobutyl, n-butyl, sec-butyl, n-hexyl, heptyl, 2-ethylhexyl, diisobutyl, isooctyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, butylphenyl,o,p-depentylphenyl, octylphenyl, polyiso-butene-(molecular weight 350)-substituted phenyl, tetrapropylene-substituted phenyl, beta-octylbutyl-naphthyl, cyclopentyl, cyclohexyl, phenyl, chlorophenyl, o-dichlorophenyl, bromophenyl, naphthenyl, 2-methylcyclohexyl, benzyl, chlorobenzyl, chloropentyl, dichlorophenyl, nitrophenyl, dichlorodecyl and xenylradicals. Alkyl radicals having about 3 to 30 carbon atoms, and aryl radicals having about 6 to 30 carbon atoms, are preferred. Particularly preferred R1 and R2 radicals are alkyl of 4 to 18 carbons.
The phosphorodithioic acids are readily obtainable by the reaction of phosphorus pentasulfide and an alcohol or phenol. The reaction involves mixing, at a temperature of about 20°C to 200°C, 4 moles of the alcohol or phenol with one mole of phosphorus pentasulfide. Hydrogen sulfide is liberated as the reaction takes place. Mixtures of alcohols, phenols or both can be employed, e.g., mixtures of C3 to C30 alkanols, C6 to C30 aromatic alcohols, etc.
The metals useful to make the phosphate salts include Group I metals, Group II metals, aluminum, lead, tin, molybdenum, manganese, cobalt and nickel. Zinc is the preferred metal. Examples of metal compounds which may be reacted with the acid include lithium oxide, lithium hydroxide, lithium carbonate, lithium pentylate, sodium oxide, sodium hydroxide, sodium carbonate, sodium methylate, sodium propylate, sodium phenoxide, potassium oxide, potassium hydroxide, potassium carbonate, potassium methylate, silver oxide, silver carbonate, magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium ethylate, magnesium propylate, magnesium phenoxide, calcium oxide, calcium hydroxide, calcium carbonate, calcium methylate, calcium propylate, calcium pentylate, zinc oxide, zinc hydroxide, zinc carbonate, zinc propylate, strontium oxide, strontium hydroxide, cadmium oxide, cadmium hydroxide, cadmium carbonate, cadmium ethylate, barium oxide, barium hydroxide, barium hydrate, barium carbonate, barium ethylate; barium pentylate, aluminum oxide, aluminum propylate, lead oxide, lead hydroxide, lead carbonate, tin oxide, tin butylate, cobalt oxide, cobalt hydroxide, cobalt carbonate, cobalt pentylate, nickel oxide, nickel hydroxide and nickel carbonate.
In some instances, the incorporation of certain ingredients, particularly carboxylic acids or metal carboxylates such as small amounts of the metal acetate or acetic acid used in conjunction with the metal reactant will facilitate the reaction and result in an improved product. For example, the use of up to about 5%
of zinc acetate in combination with the required amount of zinc oxide facilitates the formation of a zinc phosphorodithioate.
The preparation of metal phosphorodithioates is well known in the art and is described in a large number of issued patents, including U.S. Patent Nos. 3,293,181;
3,397,145; 3,396,109 and 3,442,804, insofar as the preparation of metal salts of organic phosphorodithioic acids useful in this invention are described.

Also useful as antiwear additives are amine derivatives of dithiophosphoric acid compounds, such as are described in U.S. Patent No. 3,637,499, The zinc salts are most commonly used as antiwear additives in lubricating oil in amounts of 0.1 to 10, preferably 0.2 to 2 wt. %, based upon the total weight of the lubricating oil composition. They may be prepared in accordance with known techniques by first forming a dithiophosphoric acid, usually by reaction of an alcohol or a phenol with P2S5 and then neutralizing the dithiophosphoric acid with a suitable zinc compound.
Mixtures of alcohols may be used including mixtures of primary and secondary alcohols, secondary generally for imparting improved antiwear properties, and primary for thermal stability. Mixtures of the two are particularly useful. In general, any basic or neutral zinc compound could be used but the oxides, hydroxides and carbonates are most generally employed. Commercial additives frequently contain an excess of zinc due to use of an excess of the basic zinc compound in the neutralization reaction.
The zinc dihydrocarbyl dithiophosphates are oil soluble salts of dihydrocarbyl esters of dithiophosphoric acids and may be represented by the following formula:
S
R30_~P_S Zn wherein R3 and R4 are as described in connection with the previous formula.
Suitable antiwear agents also comprise the phosphorous- and sulfur-containing product mixtures described in U.S. Patent No. 5,242,612.
In a preferred embodiment of the phosphorous- and sulfur-containing product mixtures disclosed in said commonly assigned applications, the following three components, namely: (1) organic phosphite ester, (2) hydrocarbyl thioalkanol, and (3) heterodialkanol are reacted in admixture, preferably in simultaneous admixture.
Preferred hydrocarbyl thioalkanol reactants include Cg to C18 tnioethanols.
The preferred heterodialkanols are thiodialkanols.
Representative thiodialkanols include 2,2'-thiodiethanol:
3,3'-thiodipropanol; thio-bis ethoxy-ethanol;
thiobisisopropoxyisopropanol; and mixtures thereof.
Oxidation Inhibitors Oxidation inhibitors reduce the tendency of mineral oils to deteriorate in service, which deterioration can be evidenced by the products of oxidation such as sludge and varnish-like deposits on the metal surfaces and by viscosity growth.

Useful antioxidant materials include oil soluble phenolic compounds, oil soluble sulfurized organic compounds, oil soluble amine antioxidants, oil soluble organo borates, oil soluble organo phosphites, oil soluble organophosphates, oil soluble organo dithiophosphates and mixtures thereof. Preferably such antioxidants are metal-free (that is, free of metals which are capable of generating sulfated ash), and therefore are most preferably ashless (having a sulfated ash value of not greater than 1 wt. % SASH, as determined by ASTMD874).
Illustrative of oil soluble phenolic compounds are alkylated monophenols, alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylidenebis phenols, benzyl compounds, acylaminophenols, and esters and amides of hindered phenol-substituted alkanoic acids.
Examples of Phenolic Antioxidants 1. Alkylated monophenols 2,6-di-tert-butyl-4-methylphenol; 2,6-di-tert-butylphenol; 2-tert-butyl-4,6 dimethylphenol; 2,6-di-tertbutyl-4-ethylphenol: 2,6-ditert-butyl-4-ethylphenol; 2,6-di-tert-butyl-4-n-butyl-phenol: 2,6-di-tertbutyl-4-isobutylphenol; 2,6-dicyclo-pentyl-4-methylphenol; 2-(alpha-methylcyclohexyl)-4,6-dimethylphenol; 2,6-dioctadecyl-4-methylphenol; 2,4,6-tricyclohexylphenol; 2,6-di-tert-butyl-4-methoxymethyl-phenol; o-tert-butylphenol.
2. Alkylated hydroquinones 2,6-di-tert-butyl-4-methoxyphenol: 2,5-di-tertbutyl-hydroquinone; 2,5-di-tert-amylhydroquinone: 2,6-di-phenyl-4-octadecyloxy-phenol.

_.

3. Hydroxylated thiodiphenyl ethers 2,2'-thiobis(6-tert-butyl-4-methyl-phenol); 2,2'-thiobis(4-octylphenol); 4,4'-thiobis(6-tert-butyl-3-methylphenol);
4,4'-thiobis(6-tert-butyl-2-methylphenol).
4. Alkylidenebisphenols 2,2'-methylenebis(6-tert-butyl-4-methylphenol); 2,2'-methylenebis(6-tert-butyl-4-ethylphenol); 2,2'-methylenebis[4-methyl-6-(alpha-methyl-cyclohexyl)-phenol); 2,2'-methylenebis(4-methyl-6-cyclo-hexylphenol); 2,2'-methylenebis(6-nonyl-4-methylphenol);
2,2'-methylenebis(4,6-di-tert-butyl-phenol): 2,2'-methyl-idenebis(4,6-di-tert-butylphenol); 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol); 2,2'-methylenebis[6-alpha-methylbenzyl)-4-nonylphenol]; 2,2'-methylenebis[6-(alpha, alpha-dimethylbenzyl)-4-nonyl-phenol]; 4,4'-methylene-bis(2,6-di-tert-butylphenol); 4,4'-methylenebis(6-tert-butyl-2-methylphenol); 1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)butane: 2,6-di(3-tert-butyl-5-methyl-2-hydroxy-benzyl)-4-methylphenol; 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercapobutane;
ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyl-phenyl)butyrate]; di(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene; di[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tertbutyl-4-methylpheny]terephthalate.
5. Benzyl compounds 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethyl-benzene: di(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide; 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetic acid isooctyl ester; bis(4-tert-butyl-3-hydroxy-2,6-dimethyl-benzyl)dithio-tere-phthalate: 1,3,5-tris(3,5-di-tertbutyl-4-hydroxy-benzyl)-isocyanurate1,3,5-tris(4-tertbutyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate; 3,5-di-tert-butyl-4-hydroxy-benzylphosphonic acid dioctadecyl ester 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid mono-ethyl ester calcium salt.

2111D~6 6. Acylaminophenols 4-hydroxylauric acid anilide;
4-hydroxystearic acid anilide; 2,4-bis-octylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-s-triazine; N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamic acid octyl ester.
7. Esters of beta-(3,5-di-tert-butyl-4-hydroxy-phenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol; octadecanol; 1,6-hexanediol;
neopentyl glycol; thiodiethylene glycol; diethylene glycol; triethylene glycol; pentaerythritol;
tris(hydroxy-ethyl)isocyanurate; and di(hydroxyethyl)-oxalic acid diamide.

8. Esters of beta-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol; octadecanol; 1,6-hexanediol; neopentyl glycol; thiodiethylene glycol;
diethylene glycol; triethylene glycol; pentaerythritol;
tris(hydroxyethyl)isocyanurate; and di(hydroyethyl)oxalic acid diamide.

9. Amides of beta -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, e.g., N,N'-di(3,5-di-tert-butyl-4-hydroxyphenyl-pro-prionyl)hexamethylenediamine;
N,N'-di(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) tri-methylenediamine; N,N'-di-(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)hydrazine.
Oil soluble sulfurized organic compounds include those represented by the formula:
R5Sx4R6 wherein S represents sulfur, x4 is a whole number having a value of from 1 to about 10, and R5 and R6s may be the same or different organic groups. The organic groups may be hydrocarbon groups or substituted hydrocarbon groups containing alkyl, aryl, aralkyl, alkaryl, alkanoate, thiazole, imidazole, phosphorothionate, beta-ketoalkyl groups, etc. The substantially hydrocarbon groups may contain other substituents such as halogen, amino, hydroxyl, mercapto, alkoxy, aryloxy, thio, vitro, sulfonic acid, carboxylic acid, carboxylic acid ester, etc.
Specific examples of types of sulfurized compositions which are useful. Oxidation inhibitors include aromatic, alkyl or alkenyl sulfides and polysulfides, sulfurized olefins, sulfurized carboxylic acid esters, sulfurized ester olefins, sulfurized oil, and mixtures thereof. The preparation of such oil-soluble sulfurized compositions is described in the art, (U.S. Patent No. 4,612,129), including the type and amount of reactants and catalysts (or promoters), temperatures and other process conditions, and product purification and recovery techniques (e. g., decoloring, filtering, and other solids and impurity removal steps).
The sulfurized organic compounds may be aromatic and alkyl sulfides such as dibenzyl sulfide, dixylyl sulfide, dicetylsulfide, diparaffin wax sulfide and polysulfide, cracked wax oleum sulfides, etc.
Examples of dialkenyl sulfides are described in U.S.
Patent No. 2,446,072. Examples of sulfides of this type include 6,6'-dithiobis(5-methyl-4-nonene), 2-butenyl monosulfide and disulfide, and 2-methyl-2-butenyl monosulfide and disulfide.
Representative sulfurized olefins include sulfurized olefins prepared by the reaction of an olefin (preferably containing 3 to 6 carbon atoms) or a lower molecular weight polyolefin derived therefrom, with a sulfur-containing compound such as sulfur, sulfur monochloride and/or sulfur dichloride, hydrogen sulfide, etc.
Isobutene, propylene and their dimers, trimers and tetramers, and mixtures thereof are especially preferred olefinic compounds. Of these compounds, isobutylene and diisobutylene are particularly desirable because of their availability and the particularly high sulfur-containing compositions which can be prepared therefrom.
The sulfurized organic compounds may be sulfurized oils which may be prepared by treating natural or synthetic oils including mineral oils, lard oil, carboxylic acid esters derived from aliphatic alcohols and fatty acids or aliphatic carboxylic acids (e. g., myristyl oleate and oleyl oleate) sperm whale oil and synthetic sperm whale oil substitutes and synthetic unsaturated esters or glycerides.
The sulfurized fatty acid esters can be prepared by reacting sulfur, sulfur monochloride, and/or sulfur dichloride with an unsaturated fatty ester at elevated temperatures. Typical esters include C1 to C2p alkyl esters of Cg to C24 unsaturated fatty acids such as palmitoleic, oleic, ricinoleic, petroselic, vaccenic, linoleic, linolenic, oleostearic, licanic, etc.
Sulfurized fatty acid esters prepared from mixed unsaturated fatty acid esters such as are obtained from animal fats and vegetable oils such as tall oil, linseed oil, olive oil, castor oil, peanut oil, rape oil, fish oil, sperm oil, etc. also are useful. Specific examples of the fatty esters which can be sulfurized include lauryl talate, methyl oleate, ethyl oleate, lauryl oleate, cetyl oleate, cetyl linoleate, lauryl ricinoleate, oleolinoleate, oleostearate, and alkyl glycerides.

Another class of organic sulfur-containing compounds includes sulfurized aliphatic esters of an olefinic monodicarboxylic acid. For example, aliphatic alcohols of from 1 to 30 carbon atoms can be used to esterify monocarboxylic acids such as acrylic acid, methacrylic acid, 2,4-pentadienic acid, etc. or fumaric acid, malefic acid, muconic acid, etc. Sulfurization of these esters is conducted with elemental sulfur, sulfur monochloride and/or sulfur dichloride.
Another class of sulfurized organic compounds include diester sulfides. Typical diesters include the butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, stearyl, lauryl, andeicosyl: diesters of thiodialkanoic acids such as propionic, butanoic, pentanoic and hexanoic acids. Of the diester sulfides, a specific example is dilaury1,3,3'-thiodipropionate.
Other suitable sulfurized organic compound antioxidants include those derived from a particular type of cyclic or bicyclic olefin which is a Diels-Alder adduct of at least one dienophile with at least one aliphatic conjugated diene. The sulfurized Diels-Alder adducts can be prepared by reacting various sulfurizing agents with the Diels-Alder adducts as described more fully below. Typically, the sulfurizing agent is sulfur.
The Diels-Alder adducts are a well-known, art-recognized class of compounds prepared by the diene synthesis of Diels-Alder reaction. A summary of the prior art relating to this class of compounds is found in the Russian monograph, "Dienovyi Sintes", Izdatelstwo Akademii Nauk SSSR, 1963 by A. S. Onischenko.
(Translated into the English language by L. Mandel as A.
S. Onischenko, "Diene Synthesis", N.Y., Daniel Davey and Co., Inc., 1964) ' CA 02111056 2004-05-13 Still further sulfurized organic compounds include at least one sulfurized terpene compound or a composition prepared by sulfurizing a mixture comprising at least one terpene and at least one other olefinic compound.
The term "terpene compound" as used in the specification and claims is intended to include the various isomeric terpene hydrocarbons having the empirical formula c10H16~ such as contained in turpentine, pine oil and dipentenes, and the various synthetic and naturally occurring oxygen-containing derivatives. Mixtures of these various compounds generally will be utilized, especially when natural products such as pine oil and turpentine are used. Pine oil, for example, which is obtained by destructive distillation of waste pinewood with super-heated steam comprises a mixture of terpene derivatives such as alpha-terpineol, beta-terpineol, alpha-fenchol, camphor, borneol/isoborneol, fenchone, estragole, dihydro alpha-terpineol, anethole, and other monoterpene hydrocarbons.
The specific ratios and amounts of the various components in a given pine oil will depend upon the particular source and the degree of purification. A group of pine oil-derived products are available commercially from Hercules Incorporated. The pine oil products generally known as terpene alcohols available from Hercules Incorporated are particularly useful in the preparation of this class of sulfurized products. Examples of such products include alpha-Terpineol containing about 95 to 97% of alpha-terpineol, a high purity tertiary terpene alcohol mixture typically containing 96.3% of tertiary alcohols; Terpineol* 318 Prime which is a mixture of isomeric terpineols obtained by dehydration of terpene hydrate and contains about 60 to 65 wt. % of alpha-* Trade-mark terpineol and 15 to 20% beta-terpineol, and 18 to 20% of other tertiary terpene alcohols. Other mixtures and grades of useful pine oil products also are available from Hercules under such designations as Yarmor~ 302, * ~ ~
Herco pine oil, Yarmor 302W, Yarmor F and Yarmor 60.
The above terpene compounds may be sulfurized terpene compounds, sulfurized mixtures of terpene compounds or mixtures of at least one terpene compound and at least one sulfurized terpene compound. Sulfurized terpene compounds can be prepared by sulfurizing terpene compounds with sulfur, sulfur halides, or mixtures of sulfur dioxide with hydrogen sulfide. Also, the sulfurization of various terpene compounds has been described in the prior art. For example, the sulfurization of pine oil is described in U.S. Patent No.
2,012,446.
The other olefinic compound which may be combined with the terpene compound and sulfurized may be any of several olefinic compounds such as those described earlier.
The other olefin used in combination with the terpene also may be an unsaturated fatty acid, an unsaturated fatty acid ester, mixtures thereof, or mixtures thereof with the olefins described above. The term "fatty acid" as used herein refers to acids which may be obtained by hydrolysis of naturally occurring vegetable or animal fats or oils. These fatty acids usually contain from 16 to 20 carbon atoms and are mixtures of saturated and unsaturated fatty acids. The unsaturated fatty acids generally contained in the naturally occurring vegetable or animal fats and oils may contain one or more double bonds and such acids include palmitoleic acid, oleic acid, linoleic acid, linolenic acid, and erucic acid. The unsaturated fatty acids may * Trade-mark _ 2~~,105G

comprise mixtures of acids such as those obtained from naturally occurring animal and vegetable oils such as lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil, or wheat germ oil. Tall oil is a mixture of rosin acids, mainly abietic acid, and unsaturated fatty acids, mainly oleic and linoleic acids.
Tall oil is a by-product of the sulfate process for the manufacture of wood pulp.
The most particularly preferred unsaturated fatty acid esters are the fatty oils, that is, naturally occurring esters of glycerol with the fatty acids described above, and synthetic esters of similar structure. Examples of naturally occurring fats and oils containing unsaturation include animal fats such as Neat's foot oil, lard oil, depot fat, beef tallow, etc.
Examples of naturally occurring vegetable oils include cottonseed oil, corn oil, poppyseed oil, safflower oil, sesame oil, soybean oil, sunflower seed oil and wheat germ oil.
The fatty acid esters which are useful also may be prepared from aliphatic olefinic acids of the type described above such as oleic acid, linoleic acid, linolenic acid, and behenic acid by reaction with alcohols and polyols. Examples of aliphatic alcohols which may be reacted with the above-identified acids include monohydric alcohols such as methanol, ethanol, n-propanol, isopropanol, the butanols, etc.; and polyhydric alcohols including ethylene glycol, propylene glycol, trimethylene glycol, neopentyl glycol, glycerol, etc.
The sulfurized derivatives of the other olefin compounds can be prepared by methods known in the art utilizing sulfurizing reagents such as sulfur, sulfur halides or mixtures of sulfur or sulfur dioxide with hydrogen sulfide.

2111~~~

Exemplary of amine antioxidants are phenyl-substituted and phenylene-substituted amines, N-nitro phenylhydroxylamine, isoindoline compounds, phosphinodithioic acid-vinyl carboxylate adducts, phosphorodithioate ester-aldehyde reaction products, phosphorodithioate-alkylene oxide reaction products, silyl esters of terephthalic acid, bis-1,3-alkylamino-2-propanol, anthranilamide compounds, anthranilic acid esters, alpha-methyl styrenated aromatic amines, aromatic amines and substituted benzophenones, aminoguanidines, peroxide-treated phenothiazine, N-substituted phenothiazines and triazines, 3-tertiary alkyl-substituted phenothiazines, alkylated diphenyl-amines, 4-alkylphenyl-1-alkyl-2-naphthylamines, di-benzazepine compounds, fluorinated aromatic amines, alkylated polyhydroxy benzenoid compounds, substituted indans, dimethyl octadecylphosphonate-arylimino di-alkanol copolymers and substituted benzo-diazoborole.
ExamQles of Amine Antioxidants N,N'-diisopropyl-p-phenylenediamine; N,N'-di-sec-butyl-p-phenylenediamine; N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine; N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine; N,N'-bis(1-methylheptyl)-p-phenyl-enediamine; N,N'-diphenyl-p-phenylenediamine; N,N'-di-(naphthyl-2)-p-phenylenediamine; N-isopropyl-N'-phenyl-p-phenylenediamine; N-(1,3-dimethylbutyl)-N'-phenyl-n-phenylenediamine; N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine; N-cyclohexyl-N'-phenyl-p-phenylene-diamine; 4-(p-toluenesulfonamido)diphenylamine; N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine diphenyl-amine; 4-isopropoxydiphenylamine; N-phenyl-1-naphthyl-amine; N- phenyl-2-naphthylamine; octylated diphenylamine;
4-n-butylaminophenol; 4-butyryl-aminophenol; 4-nonanoyl-aminophenol; 4-dodecanoyl-aminophenol; 4-octadecanoyl-aminophenol; di-(4-methoxy-phenyl)amine; di-tert-butyl-4-dimethylaminomethylphenol; 2,4'-diaminodiphenylmethane;
4,4'-diaminophenylmethane; N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane; 1,2-di[(2-methylphenyl)-amino]ethane; 1,2-di(phenylamino)-propane; (o-tolyl)-biguanide; di[4-(1',3'-dimethyl-butyl)phenyl]amine; tert-octylated N-phenyl-1-napthyl-amino; and mixture of mono-and dialkylated tert-butyl-/tert-octyldiphenylamines.
Oil soluble organo-borate, phosphate and phosphite antioxidants include alkyl- and aryl- (and mixed alkyl, aryl) substituted borates, alkyl- and aryl- (and mixed alkyl, aryl) substituted phosphates, alkyl- and aryl-(and mixed alkyl, aryl) substituted phosphites, and alkyl- and aryl- (and mixed alkyl, aryl) substituted dithiophosphates such as O,O,S-trialkyl dithiophosphates, O,O,S-triaryldithiophosphates and dithiophosphates having mixed substitution by alkyl andaryl groups, phosphorothionyl sulfide, phosphorus-containing silane, polyphenylene sulfide, amine salts of phosphinic acid and quinone phosphates.
A preferred class of antioxidants includes the sulfurized alkyl-substituted hydroxyaromatic compounds.
Sulfurized alkyl-substituted hydroxyaromatic compounds and the methods of preparing them are known in the art and are disclosed, for example, in the following U.S.
Patents;
U.S. Patent Nos. 2,139,766: 2,198,828; 2,230,542;
2,836,565: 3,285,854: 3,538,166; 3,844,956; 3,951,830 and 4,115,287.
In general, the sulfurized alkyl-substituted hydroxyaromatic compounds may be prepared by reacting an alkyl-substituted hydroxyaromatic compound with a sulfurizing agent such as elemental sulfur, a sulfur halide (e.g., sulfurmonochloride or sulfur dichloride), a mixture of hydrogen sulfide and sulfur dioxide, or the like. The preferred sulfurizing agents are sulfur and the sulfur halides, and especially the sulfur chlorides, with sulfur dichloride (SC12)being especially preferred.
The alkyl-substituted hydroxyaromatic compounds which are sulfurized to produce antioxidant are generally compounds containing at least one hydroxy group (e. g., from 1 to 3 hydroxy groups) and at least one alkyl radical (e.g., from 1 to 3 alkyl radicals) attached to the same aromatic ring. The alkyl radical ordinarily contains about 3 to 100, and preferably about 6 to 20, carbon atoms. The alkyl-substituted hydroxy aromatic compound may contain more than one hydroxy group as exemplified by alkyl resorcinols, hydroquinones and catechols, or it may contain more than one alkyl radical;
but normally it contains only one of each. Compounds in which the alkyl and hydroxy groups are ortho, meta and para to each other, and mixtures of such compounds, are within the scope of the invention. Illustrative alkyl-substituted hydroxyaromatic compounds are n-propylphenol, isopropylphenol, n-butylphenol, t-butylphenol, hexylphenol, heptylphenol, octylphenol, nonylphenol, n-dodecylphenol, (propenetetramer)-substituted phenol, octadecylphenol, eicosylphenol, polybutene (molecular weight about 1000)-substituted phenol, n-dodecylresorcinol and 2,4-di-t-butylphenol, and the alkyl-substituted catechols corresponding to the foregoing. Also included are methylene-bridged alkyl-substituted hydroxyaromatic compounds of the type which may be prepared by the reaction of an alkyl-substituted hydroxyaromatic compound with formaldehyde or a formaldehyde-yielding reagent such as trioxane or paraformaldehyde.

The sulfurized alkyl-substituted hydroxy-aromatic compound is typically prepared by reacting the alkyl-substituted hydroxyaromatic compound with the sulfurizing agent at a temperature within the range of about 100°C to 250°C. The reaction may take place in a substantially inert diluent such as toluene, xylene, petroleum naphtha, mineral oil, Cellosolve or the like. If the sulfurizing agent is a sulfur halide, and especially if no diluent is used, it is frequently preferred to remove acidic materials such as hydrogen halides by vacuum stripping the reaction mixture or blowing it with an inert gas such as nitrogen. If the sulfurizing agent is sulfur, it is frequently advantageous to blow the sulfurized product with an inert gas such as nitrogen or air so as to remove sulfur oxides and the like.
Also useful herein are antioxidants disclosed in the following U.S. Patents:
U.S.
Patent Nos. 3,451,166; 3,458,495; 3,470,099; 3,511,780;
3,687,848; 3,770,854; 3,850,822; 3,876,733; 3,929,654;
4,115,287; 4,136,041; 4,153,562; 4,367,152 and 4,737,301.
The most preferred antioxidants include oil soluble copper compounds. The copper may be blended into the oil as any suitable oil soluble copper compound. By oil soluble we mean the compound is oil soluble under normal blending conditions in the oil or additive package. The copper compound may be in the cuprous or cupric form.
The copper may be in the form of the copper dihydrocarbyl thio- or dithiophosphates wherein copper may be substituted for zinc in the compounds and reactions described above although 1 mole of cuprous or cupric oxide may be reacted with 1 or 2 moles of the dithiophosphoric acid, respectively. Alternatively, the copper may be added as the copper salt of a synthetic or natural carboxylic acid. Examples include C10 to C18 _~2_ 2111056 fatty acids such as stearic or palmitic, but unsaturated acids such as oleic or branched carboxylic acids such as napthenic acids of molecular weight from 200 to 500 or synthetic carboxylic acids are preferred because of the improved handling and solubility properties of the resulting copper carboxylates. Also useful are oil soluble copper dithiocarbamates of the general formula (RR'NCSS)nCu, where n is 1 or 2 and R and R' are the same or different hydrocarbyl radicals containing from 1 to 18 and preferably 2 to 12 carbon atoms and including radicals such as alkyl, alkenyl, aryl, aralkyl, alkaryl and cycloaliphatic radicals. Particularly preferred as R
and R' groups are alkyl groups of 2 to 8 carbon atoms.
Thus, the radicals may, for example, be ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-heptyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl, etc. In order to obtain oil solubility, the total number of carbon atoms (i.e., R and R') will generally be about 5 or greater.
Copper sulphonates, phenates, and acetylacetonates may also be used.
Exemplary of useful copper compound antioxidants are copper (CuI and/or CuII) salts of alkenyl carboxylic acids or anhydrides such as succinic acids or anhydrides.
The salts themselves may be basic, neutral or acidic.
They may be formed by reacting (a) any of the functionalized polymers which are useful as dispersants section, which have at least one free carboxylic acid (or anhydride) group with (b) a reactive metal compound.
Suitable acid (or anhydride) reactive metal compounds include those such as cupric or cuprous hydroxides, oxides, acetates, borates, and carbonates or basic copper carbonate.

Examples of the metal salts are Cu salts of poly-n-butene succinic anhydride (hereinafter referred to as Cu-PNBSA) polyisobutenyl succinic anhydride (hereinafter referred to as Cu-PIBSA), and Cu salts of poly-n-butene or polyisobutenyl succinic acid. Preferably, the selected metal employed is its divalent form, e.g. , Cu +
2. The preferred substrates are polyalkenyl carboxylic acids in which the alkenyl group has a molecular weight greater than about 700. The alkenyl group desirably has a M n from about 900 to 1,500, and up to 5,000. These materials can be dissolved in a solvent, such as a mineral oil, and heated in the presence of a water solution (or slurry) of the metal bearing material.
Heating may take place between 70"C and about 200"C.
Temperatures of 110"C to 140°C are entirely adequate. It may be necessary, depending upon the salt produced, not to allow the reaction to remain at a temperature above about 140°C for an extended period of time, e.g., longer than 5 hours, or decomposition of the salt may occur.
The copper antioxidants (e.g., Cu-PIBSA, Cu-PNB, Cu-oleate, or mixtures thereof) will be generally employed in an amount of from about 50 to 500 ppm by weight of the metal, in the final lubricating or fuel composition.
The copper antioxidants are inexpensive and are effective at low concentrations and therefore do not add substantially to the cost of the product. The results obtained are frequently better than those obtained with previously used antioxidants, which are expensive and used in higher concentrations. In the amounts employed, the copper compounds do not interfere with the performance of other components of the lubricating composition, in many instances, completely satisfactory results are obtained when the copper compound is the sole antioxidant in addition to the ZDDP. The copper compounds can be utilized to replace part or all of the need for supplementary antioxidants. Thus, for particularly severe conditions it may be desirable to include a supplementary, conventional antioxidant.
However, the amounts of supplementary antioxidant required are small, far less than the amount required in the absence of the copper compound.
While any effective amount of the copper antioxidant can be incorporated into the lubricating oil composition, it is contemplated that such effective amounts be sufficient to provide said lube oil composition with an amount of the copper antioxidant of from about 5 to S00 (more preferably 10 to 200, still more preferably 10 to 180, and most preferably 20 to 130 (e.g., 90 to 120)) ppm of added copper based on the weight of the lubricating oil composition. Of course, the preferred amount may depend, amongst other factors, on the quality of the basestock lubricating oil.
Corrosion Inhibitors Corrosion inhibitors, also known as anti-corrosive agents, reduce the degradation of the metallic parts contacted by the lubricating oil composition.
Illustrative of corrosion inhibitors are phosphosulfurized hydrocarbons and the products obtained by reaction of a phosphosulfurized hydrocarbon with an alkaline earth metal oxide or hydroxide, preferably in the presence of an alkylated phenol or of an alkylphenol thioester, and also preferably in the presence of carbon dioxide. Phosphosulfurized hydrocarbons are prepared by reacting a suitable hydrocarbon such as a terpene, a heavy petroleum fraction of a C2 to C6 olefin polymer such as polyisobutylene, with from 5 to 30 wt. % of a sulfide of phosphorus for 1/2 to 15 hours, at a temperature in the range of 65"C to 315"C.

_75_ Neutralization of the phosphosulfurized hydrocarbon may be effected in the manner taught in U.S. Patent No.
2,969,324.
Other suitable corrosion inhibitors include copper corrosion inhibitors comprising hydrocarbyl-thio-distributed derivatives of 1,3,4-thiadiazole, e.g., C2 to C30; alkyl, aryl, cycloalkyl, aralkyl and alkaryl-mono-, di-, tri-, tetra- or thio-substituted derivatives thereof.
Representative examples of such materials included 2,5-bis(octylthio)-1,3,4-thiadiazole; 2,5-bis(octyl-dithio)-1,3,4-thiadiazole; 2,5-bis(octyltrithio)-1,3,4-thiadiazole; 2,5-bis(octyltetrithio)-1,3,4-thiadiazole;
2,5-bis(nonylthio)-1,3,4-thiadiazole; 2,5-bis(dodecyl-dithio)-1,3,4-thiadiazole; 2-dodecyldithio-5-phenyl-dithio-1,3,4-thiadiazole; 2,5-bis(cyclohexyl dithio)-1,3,4-thiadiazole; and mixtures thereof.
Preferred copper corrosion inhibitors are the derivative of -1,3,4-thiadiazoles such as those described in U.S. Patent Nos. 2,719,125, 2,719,126 and 3,087,932;
especially preferred is the compound 2,5-bis(t-octvldithio)-1,3,4-thiadiazole commercially available as Amoco* 150, and 2,5-bis(t-nonyldithio)-1,3,4-thiadiazole, commercially available as Amoco 158.
The preparation of such materials is further described in U.S. Patent Nos. 2,719,125, 2,719,126, 3,087,932 and 4,410,436.
Corrosion inhibitors also include copper lead bearing corrosion inhibitors. Typically such compounds are the thiadiazole polysulphides containing from 5 to 50 carbon atoms, their derivatives and polymers thereof.
*Trade-mark Preferred materials are the derivatives of 1,3,4-thiadiazoles such as those described in U.S. Patent Nos.
2,719,125: 2,719,126 and 3,087,932; especially preferred is the compound 2,5 bis(t-octadithio)-1,3,4-thiadiazole, commercially available as Amoco' 150. Other similar materials also suitable are described in U.S. Patent Nos.
3,821,236: 3,904,537; 4,097,387; 4,107,059; 4,136,043;
4,188,299 and 4,193,882.
Other suitable corrosion inhibitors are the thio and polythio sulphenamides of thiadiazoles such as those described in U.K. Patent Specification 1,560,830. These compounds can be included in the lubricating composition in an amount from 0.01 to 10, preferably 0.1 to 5.0 wt. o based on the weight of the composition.
Friction Modifiers Friction modifiers serve to impart the proper friction characteristics to lubricating oil compositions such as automatic transmission fluids. Representative examples of suitable friction modifiers are found in U.S.
Patent No. 3,933,659 which discloses fatty acid esters and amides; U.S. Patent No. 4,176,074 which describes molybdenum complexes of polyisobutenyl succinic anhydride-amino alkanols: U.S. Patent No. 4,105,571 which discloses glycerol esters of dimerized fatty acids; U.S.
Patent No. 3,779,928 which discloses alkane phosphonic acid salts; U.S. Patent No. 3,778,375 which discloses reaction products of a phosphonate with an oleamide; U.S.
Patent No. 3,852,205 which discloses S-carboxy-alkylene hydrocarbyl succinimide, S-carboxy alkylene hydrocarbyl succinamic acid and mixtures thereof: U.S. Patent No.
3,879,306 which discloses N-(hydroxyalkyl) alkenyl-succinamic acids or succinimides; U.S. Patent No.
3,932,290 which discloses reaction products of di-(lower * Trade-mark alkyl) phosphites and epoxides; and U.S. Patent No.
4,028,258 which discloses the alkylene oxide adduct of phosphosulfurized N-(hydroxyalkyl) alkenyl succinimides.
Preferred friction modifiers include hydroxy amines, as disclosed in U.S. Patent No. 5,078,893 and thioether hydroxyamines, glycerol mono and dioleates; succinate esters, or metal salts thereof, of hydrocarbyl substituted succinic acids or anhydrides and thiobis alkanols such as described in U.S. Patent No. 4,344,853 and amide friction modifiers such as the reaction product of isostearic acid and tetraethylene pentamine.
Anti-Foamants Foam control can be provided by an antifoamant of the polysiloxane type, e.g. silicone oil and polydimethyl siloxane.
Rust Inhibitors Organic, oil-soluble compounds useful as rust inhibitors comprise nonionic surfactants such as polyoxyalkylene polyols and esters thereof, and anionic surfactants such as salts of alkyl sulfonic acids. Such anti-rust compounds are known and can be made by conventional means. Nonionic surfactants, useful as anti-rust additives in oleaginous compositions usually owe their surfactant properties to a number of weak stabilizing groups such as ether linkages. Nonionic anti-rust agents containing ether linkages can be made by alkoxylating organic substrates containing active hydrogens with an excess of the lower alkylene oxides (such as ethylene and propylene oxides) until the desired number of alkoxy groups have been placed in the molecule.
The preferred rust inhibitors are polyoxyalkylene polyols and derivatives thereof. This class of materials are commercially available from various sources: Pluronic*
Polyols from Wyandotte Chemicals Corporation; Polyglycol 112-2, a liquid triol derived from ethylene oxide and propylene oxide available from Dow Chemical Co.; and Tergitol, dodecylphenyl or monophenyl polyethylene glycol ethers, and Ucon, polyalkylene glycols and derivatives, both available from Union Carbide Corp. These are but a few of the commercial products suitable as rust inhibitors.
In addition to the polyols per se, the esters thereof obtained by reacting the polyols with various carboxylic acids are also suitable. Acids useful in preparing these esters are lauric acid, stearic acid, succinic acid, and alkyl- or alkenyl-substituted succinic acids wherein the alkyl or alkenyl group contains up to about 20 carbon atoms.
The preferred polyols are prepared as block polymers. Thus, a hydroxy-substituted compound, R-(OH)n (wherein n is 1 to 6, and R is the residue of a mono- or polyhydric alcohol, phenol, naphthol, etc.) is reacted with propylene oxide to form a hydrophobic base. This base is then reacted with ethylene oxide to provide a hydrophylic portion resulting in a molecule having both hydrophobic and hydrophylic portions. The relative sizes of these portions can be adjusted by regulating the ratio of reactants, time of reaction, etc., as is obvious to those skilled in the art. Typically, the ethylene oxide units will comprise from about 10 to about 40%, preferably from about 10 to about 15% by weight of the molecule. Number average molecular weight of the polyol * Trade-mark is from about 2,500 to 4,500. The polyols having a molecule weight of about 4,000 with about 10%
attributable to ethylene oxide units are particularly good.
Thus it is within the skill of the art to prepare polyols whose molecules are characterized by hydrophobic and hydrophylic moieties which are present in a ratio rendering rust inhibitors suitable for use in any lubricant composition regardless of differences in the base oils and the presence of other additives.
If more oil-solubility is needed in a given lubricating composition, the hydrophobic portion can be increased and/or the hydrophylic portion decreased. If greater oil-in-water emulsion breaking ability is required, the hydrophylic and/or hydrophobic portions can be adjusted to accomplish this.
Compounds illustrative of R-(OH)n include alkylene polyols such as the alkylene glycols, alkylene triols, alkylene tetrols, etc., such as ethylene glycol, propylene glycol, glycerol, pentaerythritol, sorbitol, mannitol, and the like. Aromatic hydroxy compounds such as alkylated mono- and polyhydric phenols and naphthols can also be used, e.g., heptylphenol, dodecylphenol, etc.
Also useful rust inhibitors are alkoxylated fatty amines, amides, alcohols and the like, including such alkoxylated fatty acid derivatives treated with Cg to C16 alkyl-substituted phenols (such as the mono- and di-heptyl, octyl, nonyl, decyl, undecyl, dodecyl arid tridecyl phenols), as described in U.S. Patent No.
3,849,501.

Demulsifiers Suitable demulsifiers include the esters disclosed in U.S. Patent Nos. 3,098,827 and 2,674,619.
Lube Oil Flow Improvers Lubricating oil flow improvers (LOFI) include all those additives which modify the size, number, and growth of wax crystals in lube oils or fuels in such a way as to impart improved low temperature handling, pumpability, and/or vehicle operability as measured by such tests as pour point and mini rotary viscometry (MRV). The majority of flow improvers are polymers or contain polymers. These polymers are generally of two types, either backbone or sidechain.
The backbone variety, such as the ethylene-vinyl acetates (EVA), have various lengths of methylene segments randomly distributed in the backbone of the polymer, which associate or cocrystallize with the wax crystals inhibiting further crystal growth due to branches and non-crystallizable segments in the polymer.
The sidechain type polymers, which are the predominant variety used as LOFI's, have methylene segments as the sidechains, preferably as straight side-chains. The polymers work similarly to the backbone type except the sidechains have been found more effective in treating isoparaffins as well as n-paraffins found in lube oils. Representative of this type of polymer are Cg to C18 dialkylfumarate/vinyl acetate copolymers, polyacrylates, polymethacrylates, and esterified styrene-maleic anhydride copolymers.

-8 ~- 21110 5 6 Seal Swell Agents Seal swellants include mineral oils of the type that provoke swelling of engine seals, including aliphatic alcohols of 8 to 13 carbon atoms such as tridecyl alcohol, with a preferred seal swellant being characterized as an oil-soluble, saturated, aliphatic or aromatic hydrocarbon ester of from 10 to 60 carbon atoms and 2 to 4 linkages, e.g., dihexyl phthalate, as are described in U.S. Patent No. 3,974,081.
Some of the above numerous additives can provide a multiplicity of effects e.g., a dispersant oxidation inhibitor. This approach is well known and need not be further elaborated herein.
Compositions, when containing these additives, typically are blended into the base oil in amounts which are effective to provide their normal attendant function.
Representative effective amounts of such additives are illustrated as follows:
(Broad) (Preferred) Compositions Wt % Wt V.I. Improver 1-12 1-4 Corrosion Inhibitor 0.01-3 0.01-1.5 Oxidation Inhibitor 0.01-5 0.01-1.5 Dispersant 0.1-10 0.1-5 Lube Oil Flow Improver 0.01-2 0.01-1.5 Detergents and Rust 0.01-6 0.01-3 Inhibitors Pour Point Depressant 0.01-1.5 0.01-1.5 Anti-Foaming Agents 0.001-0.1 0.001-0.01 Antiwear Agents 0.001-5 0.001-1.5 Seal Swellant 0.1-8 0.1-4 Friction Modifiers 0.01-3 0.01-1.5 Lubricating Base Oil Balance Balance When other additives are employed, it may be desirable, although not necessary, to prepare additive ~~~~056 concentrates comprising concentrated solutions or dispersions of the subject additives of this invention (in concentrate amounts hereinabove described), together with one or more of said other additives (said concentrate when constituting an additive mixture being referred to herein as an additive-package) whereby several additives can be added simultaneously to the base oil to form the lubricating oil composition. Dissolution of the additive concentrate into the lubricating oil may be facilitated by solvents and by mixing accompanied with mild heating, but this is not essential. The concentrate or additive package will typically be formulated to contain the additives in proper amounts to provide the desired concentration in the final formulation when the additive package is combined with a predetermined amount of base lubricant. Thus, the subject additives of the present invention can be added to small amounts of base oil or other compatible solvents along with other desirable additives to form additive-packages containing active ingredients in collective amounts of typically from about 2.5 to about 90%, and preferably from about 15 to about 75%, and most preferably from about 25 to about 60% by weight additives in the appropriate proportions with the remainder being base oil.
The final formulations may employ typically about 10 wt. % of the additive-package with the remainder being base oil.
All of said weight percents expressed herein (unless otherwise indicated) are based on active ingredient (A. I.) content of the additive, and/or upon the total weight of any additive-package, or formulation which will be the sum of the A.I. weight of each additive plus the weight of total oil or diluent.

The improved process of this invention can be further illustrated by reference to the following examples, wherein parts are by weight unless otherwise indicated.
EXAMPLE
PIBSA-PAM
Unless otherwise indicated, Examples and Comparative Examples used the following general procedure to make polyisobutylene succinimide (PIBSA-PAM).
A polyisobutylene succinic anhdyride (PIBSA) of known composition, SAP number = 37, BS&W sediment = 0.004 volume %, 625 grams of PIBSA was charged to a round bottom reaction flask. To that PIBSA, 95.9 parts of a neutral 150 weight petroleum basestock was added. The reactor had a "half moon" or crescent shaped agitator blade coupled with an electric drive variable speed motor with a digital readout in revolutions per minute. The desired speed was programmed into the drive unit and the motor maintained this RPM during the reaction. This was 150 RPM unless otherwise indicated. An electric heating mantle was attached to the bottom of the reactor and via either a thermocouple or mercury thermometer/optical switch arrangement, a signal was sent to a temperature controller which in turn varied the voltage to the heating mantle. A desired setpoint was entered or set on the control mechanism. The reaction mixture was maintained at all times under a nitrogen blanket to prevent oxidation of the neutral basestock oil diluent at high temperatures. The temperature controller was set at 128°C and when the reaction mass was at about 40°C, the agitator drive was set to the specified RPM which was varied for individual experiments. Once the reaction mass had reached 128°C, the polyamine (PAM) addition ... 2111056 began. Using a graduated dropping funnel with a sidearm, 21.6 grams of PAM was charged to the funnel. PAM was charged to the reaction mass in quarter volume charges using the graduated markings on the funnel as a guide.
At time equal to zero, 25% of the PAM required was added by volume into the reactor. The reactor soaked for 15 min. at this temperature under agitation and then the 25%
volume addition sequence and time was repeated until all the PAM was consumed. The reactor soaked for an additional 30 min. under a nitrogen sweep or blanket condition.
Boration of PIBSA-PAM
Unless otherwise indicated, the following procedure was used to borate the PIBSA-PAM.
The reaction then entered the boration phase. A
boric acid slurry was prepared by either using a commercially available boric acid or subjecting an available boric acid to a wet or dry milling technique to reduce the particle size. Then a neutral basestock was added either to the resulting dry milled powder, the commercially available dry boric acid, or milled boric acid paste to form a desired weight percent of boric acid slurry in oil. This slurry was charged into four small addition beakers which were each contained to 25% by weight of the total desired mass. At the conclusion of a 30 min. soak period the reactor was maintained at 128"C
and the first addition of boric acid was added to the mixture. One half hour later, the second addition was added and the reactor then allowed to soak an additional 30 min. This procedure was repeated until all of the boric acid was consumed. The reactor was allowed to soak an additional hour after the last addition of boric acid ~.. 2111~5~
_g5_ under a nitrogen blanket or seep. The product was then ready for use.
Example 1 The above described PIBSA-PAM was borated using the low temperature amination boration process described in detail. A dry milled boric acid was provided by a manufacture using their own internal proprietary methods.
This milled boric acid was then slurried in a petroleum basestock and used to borate the PIBSA-PAM in the manner described above. 11.6 grams of boric acid slurry was added to the 66.0 gram feedstock to form a 15 wt. % boric acid in oil compound. A particle size measurement was taken of the slurry as well. As shown in Table I, this resulted in a measured ~ of 327 for the starting boric acid and BS&W sediment level on the resulting product of 0.016 volume %.
Example 2 Using the low temperature amination boration process described, a lab milled boric acid was provided made using a one horsepower high shear disperser manufactured by Ross Co. by making a slurry of granular boric acid in petroleum oil and mixing it in the apparatus. This milled boric acid was then used to borate the PIBSA-PAM
in the manner described above. 11.6 grams of boric acid slurry was added to the 66.0 gram feedstock to form a 15 wt. % boric acid in oil compound. A particle size measurement was taken of the slurry as well. This resulted in a measured ~ of 415 for the starting boric acid and BS&W sediment level on the resulting product of 0.016 volume %.

211105 fi Example 3 Using the standard low temperature amination boration process described, a commercially available pharmaceutical grade of very fine boric acid was obtained from a supplier and intimately mixed in a high speed industrial blender for 5 min. in the presence of a petroleum basestock. This boric acid suspension was then used to borate the PIBSA-PAM in the manner described above. 11.6 grams of boric acid slurry was added to the 66.0 gram feedstock to form a 15 wt. o boric acid in oil compound. A particle size measurement was taken of the slurry as well. This resulted in a measured v~ of 423 for the starting boric acid and BS&W sediment level on the resulting product of 0.02 volume %.
ExamQle 4 Using the standard low temperature amination boration process described in detail (a resin kettle or U-shaped reactor was used instead of a round bottom reaction flask), a pilot plant milled boric acid was provided using a twenty five horsepower high shear disperser manufactured by the Goodway Co. which was fed continuously with a feed of slurried boric acid in oil.
The amination reactor agitator operated at 150 rpm, and the boration reactor agitator operated at 250 rpm. This milled boric acid was then used to borate the PIBSA-PAM
in the manner described above. 11.6 grams of boric acid slurry was added to the 66.0 gram feedstock to form a 15 wt. % boric acid in oil compound. A particle size measurement was taken of the slurry as well, although it had a high contamination of granular boric acid which made an accurate acquisition of the particle size distribution difficult. This resulted in a measured m of 440 for the starting boric acid and BS&W sediment level on the resulting product of 0.03 volume %.
Comparative Example 5 Using the standard low temperature amination boration process described (a resin kettle or U-shaped reactor was used instead of a round bottom reaction flask), a pilot plant milled boric acid was provided using a ten horsepower high shear disperser manufactured by the Silverson Co. which was feed continuously with a feed of slurried boric acid in oil. The reactor agitators in both the amination reactor and boration reactor were operated at 800 rpm. This milled boric acid was then used the in the manner described in the procedure. 11.6 grams of boric acid slurry was added to the 66.0 gram feedstock to form a 15 wt. % boric acid in oil compound. A particle size measurement was taken of the slurry as well, although it had a high contamination of granular boric acid which made an accurate acquisition of the particle size distribution difficult due to flow cell plugging. This resulted in a measured o of 500 for the starting boric acid and BS&W sediment level on the resulting product of 0.04 volume %.
Comparative Example 6 Using the standard low temperature amination boration process described in detail, a commercially available powdered grade of boric acid was obtained from a supplier and intimately mixed in a high speed industrial blender for 5 min. in the presence of a petroleum basestock. This boric acid slurry was then used in the manner described in the procedure. 11.6 grams of boric acid slurry was added to the 66.0 gram 211105 fi _88_ feedstock to form a 15 wt. % boric acid in oil compound.
A particle size measurement was taken of the slurry as well. It was found however, that there was a very high contamination of granular boric acid in this material which made conventional particle size analysis very difficult due to plugging. The powdered material was passed through a 40 mesh sieve screen which resulted in about 10 wt. o of the mass being retained on the screen.
This solid which passed through the screen was then slurried and analyzed. The missing 10 wt. % of mass was then mathematically added back into the particle size distribution by assuming that it was 600 microns and calculating its area and volume based on that number.
This resulted in an estimated o of 625 for the starting boric acid and BS&W sediment level on the resulting product of 0.08 volume %.
Example 7 A spherical vessel is charged with 863.1 grams of 2200 MW PIBSA and S150N base oil and heated to 115°C. To that mass, 23.7 grams of polyamine is added over a one hour time period. The material is stripped with nitrogen for one half hour and the mass is then heated to a temperature of 149"C. To this reaction mass is added a milled suspension of boric acid. The milling was accomplished in a separate vessel by adding solid boric acid to oil and maintaining it at 100°C under high shear conditions for over an hour. The milled boric acid had a o~ of 415. 78.3 grams of this slurry at 15% solids was added over a one hour time period and the resulting product stripped with nitrogen at the temperature of one hour. The reactor was sampled and some of the raw product was added to 50 ml of heptane in a BS&W tube.
The tube was spun at 1800 rpm in a centrifuge for a period of one hour. The resulting sediment product on the bottom was measured as volume percent of the total tube volume and doubled to correct for the solvent dilution effect. A sediment level of 0.016 vol.
resulted with a filtered boron content of 0.25% and an ASTM D-1500 color of 2.0 at a 15% weight dilution in white oil.
Comparative Example 8 To the same reaction step as above, the equivalent PIBSA oil reaction charges were added to the reactor.
The reactor was heated to a temperature of 149°C and the same amount of PAM was added in an identical manner. The reactor was then heated to a temperature of 163°C. For the boration step, a conventional granular solid form of boric acid is added. This is believed to have a of of greater than 1200. The boric acid was added over an identical time period and the reactor stripped in an identical manner. The resulting sediment was measured at 0.3 vol. % with a filtered boron percent of 0.19 and a color of 2.5.
Comparative Example 9 To the same reaction setup and charges, the reactor is heated to 149°C, aminated, stripped and maintained at 149°C. Granular boric acid was added to the reactor at that temperature over the same time internal and stripped for the same time period. This is believed to have a of greater than 1200. The resulting sediment was 0.6 vol. % with a filtered boron content of 0.19% and a color of 3Ø

Comparative Example 10 The same reaction setup and charges are accomplished with an amination temperature of 135°C. Granular boric acid slurry in petroleum basestock was added at the same temperature, reacted and stripped. The raw sediment was 0.038 vol. % with a filtered boron percent equalling 0.22.
Example 11 The same reaction setup and charges were aminated at a temperature of 115°C. The reactor was heated to a temperature of 135°C. The milled boric acid (a~ of 415) suspension was added at that temperature, reacted and stripped in an identical manner. The raw sediment was measured at a wt. % 0.01 vol. % with a filtered boron content of 0.22%.
As can be concluded from the above experiments, the amination temperature, boration temperature and the use of a milled suspension of boric acid are variables in producing a low sediment product. It can also be observed that process borates the molecule more efficiently and to a higher level than can be accomplished by conventional techniques. The more efficient boration technique also neutralizes the basicity of the dispersant molecule to a higher degree as evident by the higher boron content. It is theorized that this suppresses the interaction between the dispersant and the unsaturation in the base oil leading to a lower color dispersant.
The principles, preferred embodiments, and modes of operation of the present invention have been described in the foregoing specification. The invention which is z~~lo~s intended to be protected herein, however, is not to be construed as limited to the particular forms disclosed, since these are to be regarded as illustrative rather than restrictive. Variations and changes may be made by those skilled in the art without departing from the spirit of the invention.

TABLE I - Determination of ~ Value for Example 1 Distributiond N Sphere VolumeSphere Surface Segment (4/3 Nnd3) Area microns (Nnd2~

4-6 5 0.07 3.67 * 101 5.5 6 - g 7 0.31 4.45 * 102 4.77 * 101 8 - l0 9 0.55 1.68 * 103 1.40 * 102 - 14 ~ 12 0.93 ~ 6.73 * 103 4.21 * 102 ~

14 - 20 ~ 1.25 * 104 5.54 * 102 l7 0.61 ~
~

- 30 25 1.03 6.74 * 104 2.02 * 103 - 40 35 I 1.68 3.02 * 105 6.47 * 103 - 50 45 2.02 7.71 * 105 1.29 * 104 - 60 ~ 55 1.54 1.07 * 106 1.46 * 104 - 70 65 1.21 1.39 * l06 1.61 * 104 - 80 75 1.62 2.86 * 106 2.86 * 104 - 90 ~ 85 2.06 5.30 * 106 4.68 * 104 - 100 95 2.79 1.00 * 107 7.91 * 104 100 - 150 ~ 125 22.36 1.83 * 108 1.10 * 106 150 - 200 ~ 6.42 * 2.75 * 106 ~ 175 ~ 108 28.6 200 - 300 250 27.08 1.77 * l09 5.32 * 106 300 - 400 8.14 * 108 1.74 * 106 ~ 350 4.53 400 - 500 .150 0.89 3.40 * 108 5.66 * 105 500 - 600 ~ 550 0.12 8.36 * 107 1.14 * 105 Total 100 3.86 * 109 1.18 * 107 value = 327 d = average particle diameter of the distribution segment.
N = the particle volume percent of the distribution segment.

Claims (15)

1. An improved low sediment process for forming a borated oil soluble polymer-substituted nitrogen- or ester-containing lubricating oil additive which comprises (a) contacting a non-borated polymer-substituted nitrogen- or ester-containing additive in the presence of a solvent therefore, under boronating reaction conditions in a reaction zone with particulate boric acid having an average particle size distribution in lubricating oil characterized by a .slzero. value of not greater than 450, wherein said .slzero. value is the ratio of said particles' total spherical volume divided by said particles' total spherical external surface area, and (b) recovering said borated additive.

2. The process according to claim 1 wherein said polymer-substituted additive comprises a polyalkenyl-substituted succinimide.

3. The process according to claim 2 wherein said polyalkenyl-substituent comprises polyisobutenyl.

4. The process according to claim 1 wherein said .slzero. value is from 200 to 450.

5. The process according to claim 1 wherein said .slzero. value is from 300 to 430.

6. The process according to claim 1 wherein said solvent comprises mineral lubricating oil.

7. The process according to claim 1 wherein said boric acid particles are charged to said reaction zone as a lubricating oil slurry or suspension.

8. The process according to claim 1 wherein said boric acid particles have a particle size range of from 350 to 430 microns.

9. The process according to claim 1 wherein said contacting is effected at a temperature of from 100 to 170°C.

10. The process according to claim 1 wherein said contacting is effected at a temperature of from 110 to 150°C.

11. The process according to claim 9 wherein said contacting is conducted in an invert atmosphere.

12. The process according to claim 1 wherein said borated additive contains up to 5 wt.% boron.

13. The process according to claim 1 wherein from 0.35 to 85 parts by weight of said boric acid are charged to said reaction zone per part by weight of said non-borated polymer-substituted additive.

14. The process according to claim 1 wherein said recovered borated additive contains less than 0.03 vol.% sediment.

15. The process according to claim 1 further comprising forming the nitrogen substituted polymer by animating the polymer at a temperature of from 115 to 135°C.